Method of making an amino silicone nanoemulsion

ABSTRACT

The present invention relates to a method of making an amino silicone nanoemulsions. More specifically, the present invention relates to a method of making an amino silicone nanoemulsions that may be used to protect surfaces from being soiled or wetted.

FIELD OF THE INVENTION

The present invention relates to a method of making an amino siliconenanoemulsion. More specifically, the present invention relates to amethod of making an amino silicone nanoemulsion that may be used toprotect surfaces from being soiled or wetted.

BACKGROUND OF THE INVENTION

Numerous attempts have been made to develop a treatment composition thatprovides protection of surfaces by repelling water and oil based soilsfrom the surface. Fluoropolymers, such as those used in Scotchguard®from 3M, have become well established as soil-repellant molecules.However, fluoropolymers are not preferred due to environmental, andhealth and safety concerns, such as potential and possibility ofpersistent bioaccumulation and toxicity.

The combination of polyorganosiloxane fluids and silicone resins inattempts to treat hard or soft surfaces is also known. Silicone resinsare highly cross-linked silicone materials that have very highviscosities. These materials are generally difficult to handle in amanufacturing environment and difficult to formulate with, given theirhigh viscosities. And, incorporating compositions containing siliconeresins into liquid-based and emulsion-based treatment formulationsgenerally requires high energy processes.

Silicone lattices, where crosslinking in emulsion occurs by means of acondensation reaction, addition reaction, or free-radical polymerizationreaction, are known. Self-crosslinking silicone emulsions, wherecrosslinking occurs via acetoxy, aminoxy, acetamido, carboxyl,cycloalkyl, or oxime groups, are known. And, emulsions andmicroemulsions of amino-functional organosiloxanes and di- and/oroligo(meth)acrylates, and their Michael addition products are alsoknown.

Unfortunately, to date, the attempts at non-fluorpolymer protection ofsurfaces continue to demonstrate disadvantages, including lowefficiency, difficulty in achieving the desired benefits at affordablecost and in a preferred format, processing and formulation challenges,and product instability. A continued need exists for a non-fluoropolymertechnology that delivers depositable benefits to surfaces, such as waterand oily soil repellency, in a convenient form and at a high efficiency.

SUMMARY OF THE INVENTION

The present invention attempts to solve one more of the needs byproviding a method of making an amino silicone nanoemulsion comprisingthe steps of:

-   -   a) mixing one or more liquid amino silicone compounds        represented by formula (1) below with a solvent:

-   -   where each R is an alkyl group or a phenyl group with 1-10        carbon atoms,    -   wherein each R′ is an alkyl group having 1-10 carbon atoms, a        phenyl group, a monovalent group represented by formula (2)        below, or a monovalent group represented by the formula: —OR³,        where R³ is a hydrogen atom or a monovalent hydrocarbon group        with 1-10 carbon atoms; m is a whole number from 50-1000, n is a        whole number from 1-100,        -   A is a monovalent group represented by formula (2) below:

—R¹—(NH—R²)a-NH₂  (2)

-   -   where R¹ and R² are divalent hydrocarbon groups with 1-10 carbon        atoms; a is a whole number from 0-4;    -   b) mixing the mixture of amino silicone and solvent with        surfactant, water, and, optionally, a protonating agent, to form        a nanoemulsion;    -   c) dividing the nanoemulsion into a first nanoemulsion and a        second nanoemulsion;    -   d) mixing the second nanoemulsion with a non-resin crosslinking        agent        -   i. at a temperature ranging from about 20° C. to about 100°            C.;        -   ii. wherein the non-resin crosslinking agent is represented            by formula (3):

R-L_(n)  (3)

-   -   -   -   wherein n≧2, R is a polyvalent, saturated or                unsaturated, substituted or unsubstituted, organic                moiety comprising 2-30 carbon atoms, and the L groups,                which may be identical or different, are functional                groups capable of reacting with amino groups;

        -   iii. wherein the molar ratio of the non-resin crosslinking            agent to the liquid amino silicone compound in the second            nanoemulsion is from about 0.05:1 to about 10:1, preferably            from about 0.1:1 to about 5:1, more preferably from about            0.5:1 to about 3:1;

    -   e) mixing the first nanoemulsion with the second nanoemulsion to        form a third nanoemulsion.

The invention also relates to methods of using the amino siliconenanoemulsions that are made by the described methods, as well as methodsof making treatment compositions comprising the amino siliconenanoemulsions and methods of treating surfaces with treatmentcompositions comprising the amino silicone nanoemulsions.

DETAILED DESCRIPTION OF THE INVENTION

Features and benefits of the various embodiments of the presentinvention will become apparent from the following description, whichincludes examples of specific embodiments intended to give a broadrepresentation of the invention. Various modifications will be apparentto those skilled in the art from this description and from practice ofthe invention. The scope is not intended to be limited to the particularforms disclosed and the invention covers all modifications, equivalents,and alternatives falling within the spirit and scope of the invention asdefined by the claims.

As used herein, the articles including “the,” “a” and “an” when used ina claim or in the specification, are understood to mean one or more ofwhat is claimed or described.

As used herein, the terms “include,” “includes” and “including” aremeant to be non-limiting.

The term “substantially free of” or “substantially free from” as usedherein refers to either the complete absence of an ingredient or aminimal amount thereof merely as impurity or unintended byproduct ofanother ingredient. A composition that is “substantially free” of/from acomponent means that the composition comprises less than about 0.5%,0.25%, 0.1%, 0.05%, or 0.01%, or even 0%, by weight of the composition,of the component.

As used herein, the term nanoemulsion refers to thermal dynamicallystable oil in water emulsions that have extremely small droplet sizes(below 350 nm, or typically below 250 nm). These materials have specialproperties, including optical translucency, very large dispersed phasesurface-to-volume ratios and long term kinetic stability. Due tosimilarity in appearance, translucent nanoemulsions are sometimesconfused with microemulsions, which belong to another class of stable(thermodynamically) and optically clear colloidal systems.Microemulsions are spontaneously formed by “solubilizing” oil moleculeswith a mixture of surfactants, co-surfactants and co-solvents. Therequired surfactant concentration in a microemulsion is several timeshigher than that in a nanoemulsion and significantly exceeds theconcentration of the dispersed phase (generally, oil). Because of manyundesirable side-effects caused by surfactants, this is disadvantageousor prohibitive for many applications. In addition, the stability ofmicroemulsions is easily compromised by dilution, heating, or changingpH levels.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

All cited patents and other documents are, in relevant part,incorporated by reference as if fully restated herein. The citation ofany patent or other document is not an admission that the cited patentor other document is prior art with respect to the present invention.

In this description, all concentrations and ratios are on a weight basisof the cleaning composition unless otherwise specified.

Method of Making an Amino Silicone Nanoemulsion

The present invention relates to a method of making an amino siliconenanoemulsion comprising the steps of:

-   -   a) mixing one or more liquid amino silicone compounds        represented by formula (1) below with a solvent:

-   -   where each R is an alkyl group or a phenyl group with 1-10        carbon atoms,    -   wherein each R′ is an alkyl group having 1-10 carbon atoms, a        phenyl group, a monovalent group represented by formula (2)        below, or a monovalent group represented by the formula: —OR³,        where R³ is a hydrogen atom or a monovalent hydrocarbon group        with 1-10 carbon atoms; m is a whole number from 50-1000, n is a        whole number from 1-100,        -   A is a monovalent group represented by formula (2) below:

—R¹—(NH—R²)a-NH₂  (2)

-   -   where R¹ and R² are divalent hydrocarbon groups with 1-10 carbon        atoms;    -   a is a whole number from 0-4;    -   b) mixing the mixture of amino silicone and solvent with        surfactant, water, and, optionally, a protonating agent, to form        a nanoemulsion;    -   c) dividing the nanoemulsion into a first emulsion and a second        emulsion;    -   d) mixing the second emulsion with a non-resin crosslinking        agent        -   i. at a temperature ranging from about 20° C. to about 100°            C.;        -   ii. wherein said non-resin crosslinking agent is represented            by formula (3):

R-L_(n)  (3)

-   -   -   -   wherein n≧2, R is a polyvalent, saturated or                unsaturated, substituted or unsubstituted, organic                moiety comprising 2-30 carbon atoms, and the L groups,                which may be identical or different, are functional                groups capable of reacting with amino groups;

        -   iii. wherein the molar ratio of the non-resin crosslinking            agent to the liquid amino silicone compound in the second            emulsion is from about 0.05:1 to about 10:1, preferably from            about 0.1:1 to about 5:1, more preferably from about 0.5:1            to about 3:1;

    -   e) mixing the first nanoemulsion with the second nanoemulsion to        form a third nanoemulsion.

The first nanoemulsion may be substantially free of a non-resincrosslinking agent.

In the methods described herein, the protonating agent may be mixed inbefore the step of mixing in the non-resin crosslinking agent. Or, theprotonating agent may be mixed in after the step of mixing in thenon-resin crosslinking agent. Example 1 (below) describes mixingprotonating agent with a mixture of amino silicone and solvent,surfactant, and water, to form a nanoemulsion and then mixing thenanoemulsion with a crosslinker to produce a resulting nanoemulsion thathas a reduced particle size. Example 2 (below) describes mixing amixture of amino silicone and solvent with surfactant and water, to forman emulsion, then mixing this emulsion with a crosslinker, and finallymixing in a protonating agent to form the resulting nanoemulsion. Theresulting nanoemulsions, in Example 2, have increased particle sizes, ascompared to Example 1.

The method may further comprise the step of mixing the firstnanoemulsion with a non-resin crosslinking agent:

-   -   i. at a temperature ranging from about 20° C. to about 100° C.;    -   ii. wherein the non-resin crosslinking agent is represented by        formula (3):

R-L_(n)  (3)

-   -   -   wherein n≧2, R is a polyvalent, saturated or unsaturated,            substituted or unsubstituted, organic moiety comprising 2-30            carbon atoms, and the L groups, which may be identical or            different, are functional groups capable of reacting with            amino groups;

    -   iii. wherein the molar ratio of the non-resin crosslinking agent        to the liquid amino silicone compound in the first emulsion is        from about 0.05:1 to about 10:1, preferably from about 0.1:1 to        about 5:1, more preferably from about 0.5:1 to about 3:1.        When the method further comprises the step of mixing the first        nanoemulsion with a non-resin crosslinking agent, the ratio of        the non-resin crosslinking agent to the liquid amino silicone        compound in the first emulsion may be different from the ratio        of the non-resin crosslinking agent to the liquid amino silicone        compound in the second emulsion.

The ratio of the first nanoemulsion to the second nanoemulsion in thethird nanoemulsion may be from about 1:1 to about 12:1, preferably about6:1.

Each of the first, second, and the third nanoemulsion may besubstantially free of a silicone resin.

Amino Silicone Nanoemulsion

The amino silicone nanoemulsions made by the method disclosed hereinprovide a highly efficient deposition on a target surface. Benefitsderived from this deposition may generally apply in the area ofrepellency of water and/or water-based compositions and/or oil and/oroil-based compositions, such as water-based stains and oily soils. Suchbenefits may be measured as an increased time to wick on fabrics, areduced dry-time on hair and/or an increased contact angle on a hardsurface. Without being bound by theory, it is believed that the aminosilicone nanoemulsions disclosed herein comprise self-assembled,spherical, positively charged amino silicone nano-particles. Theseself-assembled, spherical, positively charged nano-particles exhibitefficient deposition and controlled spreading, forming a structured filmon a surface that provides the repellency benefit. It is believed thatcrosslinking of the amino silicone nanoemulsion (e.g., at the ratio(s)of non-resin crosslinking agent to amino silicone compound describedherein) further enhances the repellency benefits. And, mixingnanoemulsions having different degrees of crosslinking (in other words,different ratios of non-resin crosslinking agents to liquid aminosilicone compounds) further enhances repellency.

The average particle sizes of the disclosed nanoemulsions range fromabout 20 nm to about 350 nm, or about 20 nm to about 250 nm, or about 20nm to about 200 nm, or about 30 nm to about 140 nm, or about 50 nm toabout 100 nm. (as measured by Malvern Zetasizer Nano Seriesinstrument.).

Amino Silicone Compound

The amino silicone nanoemulsion of the present invention comprises fromabout 1% to about 45% of one or more liquid amino silicone compounds, byweight of the nanoemulsion. The amino silicone nanoemulsion may comprisefrom about 5% to about 30% of the amino silicone compounds, by weight ofthe nanoemulsion. The amino silicone nanoemulsion may comprise fromabout 10% to about 20% of the amino silicone compounds, by weight of thenanoemulsion.

The amino silicone compound may be represented by structural formula (1)below:

where each R group is independently selected from substituted orunsubstituted alkyl or aryl groups having 1-22 carbon atoms, each R′group is independently selected from substituted or unsubstituted alkylor aryl groups having 1-22 carbon atoms, or monovalent groupsrepresented by the formula: —OR³, where R³ is a hydrogen atom or amonovalent hydrocarbon group with 1-10 carbon atoms; m is a whole numberfrom 20-1000, typically m is a whole number from 50-800; n is a wholenumber from 1-100, typically n is a whole number from 5-80.

A is a monovalent group represented by formula (2) below:

R¹—(NH—R²)_(a)—NH₂  (2)

where each of R¹ and R² is independently selected from divalenthydrocarbon groups having 1-22 carbon atoms, more typically 1-8 carbonatoms, even more typically 1-4 carbon atoms. Suitable R¹ and R² groupsinclude methylene groups, ethylene groups, trimethylene groups,tetramethylene groups, or other alkylene groups. Each of R¹ and R² maybe a methylene group; a is a whole number from 0-4, typically a is awhole number from 0-2, more typically, a is 0 or 1.

One species of amino silicone compound may be used alone or two or morespecies may be used together.

Examples of suitable A groups include —CH₂—NH₂, —(CH₂)₂—NH₂,—(CH₂)₃—NH₂, —(CH₂)₂—NH—(CH₂)₃NH₂, —(CH₂)₃—NH—(CH₂)₂NH₂,—(CH₂)₃—HN—(CH₂)₃NH₂, and —(CH₂)₃—NH—(CH₂)₃—NH—(CH₂)₃—NH₂.

In the amino silicone compound of formula (1), the ratio of m/n may beless than about 100, or m/n is less than about 90, or m/n is less thanabout 80.

The amino silicone compound may be represented by general formula (1),where each R is a methyl group, each R′ is a methyl group, A is a propylamino, and m/n is about 70.

From about 1% to about 20% of the terminal R′ groups in the aminosilicone compound represented by general formula (1) may be monovalentgroups represented by the formula: —OR³, where R³ is a hydrogen atom ora monovalent hydrocarbon group with 1-10 carbon atom.

The viscosity of the amino silicone compound may be from about 10 mPa·s,at 25° C., or from about 50 mPa·s, to about 100,000 mPa·s, or to about10,000 mPa·s. The polyorgansiloxane compound may have a viscosity offrom about 200 mPa·s to about 500 mPa·s, at 25° C.

Non-Resin Crosslinking Agent

Non-resin crosslinking agents (also referred to herein as non-resincrosslinkers) are molecules with two or more functional groups that joinchains of amino silicones. Without being bound by theory, it is believedthat the crosslinking agent covalently binds to the amino silicone viathe amino group. Thus, the crosslinking agent may be difunctional,trifunctional, tetrafunctional, or otherwise polyfunctional. A varietyof crosslinking agents may be used in the amino silicone nanoemulsion.

The non-resin crosslinking agent may be represented by formula (3):

R-L_(n)  (3)

wherein n≧2, R is a polyvalent, saturated or unsaturated, substituted orunsubstituted, organic moiety comprising 2-30 carbon atoms, and the Lgroups, which may be identical or different, are functional groupscapable of reacting with amino groups;

Nonlimiting examples of L groups include saturated or unsaturated,substituted or unsubstituted alkyl, aryl, alkyl-aryl halides,substituted or unsubstituted, saturated or unsaturated C₁-C₃₀ esters,substituted or unsubstituted di(meth)acrylates or oligo(meth)acrylates,substituted or unsubstituted C₁-C₃₀ acrylates, and substituted orunsubstituted C₁-C₃₀ epoxides.

R may be a polyvalent, saturated or unsaturated, substituted orunsubstituted, organic moiety comprising 2-15 carbon atoms, preferably apolyvalent, saturated or unsaturated, substituted or unsubstituted,alkyl group comprising 2-15 carbon atoms, more preferably a polyvalent,saturated or unsaturated, substituted or unsubstituted, alkyl groupcomprising 2-10 carbon atoms. The non-resin crosslinking agent offormula (3) may comprise at least two identical L groups.

The non-resin crosslinking agent may be selected from the groupconsisting of alkyl poly-halides, preferably alkyl dihalides, morepreferably C₂-C₃₀ alkyl dihalides, saturated or unsaturated esters, forexample, saturated or unsaturated diesters, preferably saturated orunsaturated C₂-C₃₀ diesters, more preferably C₂-C₃₀ dimethylesters,C₂-C₃₀ diethylesters, and C₂-C₃₀ divinyl esters, saturated orunsaturated C₂-C₃₀ di-, tri-, and polycarboxylic acids, substituted orunsubstituted epoxides, preferably diepoxides, more preferably C₂-C₃₀diepoxide, substituted or unsubstituted acrylates, preferablysubstituted or unsubstituted di(meth)acrylates or oligo(meth)acrylates,and mixtures thereof. The non-resin crosslinking agent may be selectedfrom the group consisting of alkyl di-iodides, alkyl dichlorides, alkyldibromides, and mixtures thereof. The non-resin crosslinking agent maybe selected from the group consisting of dibromopropane,1,4-dibromobutane, 1,6-dibromohexane, 1,12-dibromo-dodecane,1,4-dichloro-2-butene, dichloro-o-xylene, dichloro-m-xylene,dichloro-p-xylene, and mixtures thereof. The non-resin crosslinkingagent may be selected from the group consisting of activated esters, forexample, vinyl esters of di-, tri-, or poly-acid compounds, such asdivinyladipate. The non-resin crosslinking agent may be selected fromthe group consisting of dimethyl adipate (DMA), divinyl adipate (DVA),and mixtures thereof.

The non-resin crosslinking agent may be selected from the groupconsisting of etheylene glycol diepoxide, propylylene glycol diepoxide,hexanediol diepoxide, epichlorohydrin, and butanediol diepoxide.

The non-resin crosslinking agent may be selected from C₁-C₃₀ alcoholesters of carboxylic acids, such as citric acid or C₂-C₃₀ dicarboxylicacids, e.g., oxalic acid, malonic acid, succinic acid, glutaric acid,adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.

Suitable examples of unsubstituted di(meth)acrylates are: hexanedioldiacrylate, butanediol diacrylate, GX-8370 (Siber-Hegner),1,3-butanedioldimethacrylate, and neopentyl glycol diacrylate.

Suitable examples of substituted di(meth)acrylates are: 1-acryloxy2-hydroxy 3-methacryloxpropane, 2,2-dimethylpropyl2,2-dimethylpropionate diacrylate, pentaerythritol diacrylatemonostearate, polyethylene glycol-400 diacrylate, polyethyleneglycol-300 diacrylate, polypropylene glycol-400 diacrylate,tetraethylene glycol diacrylate, polypropylene glycol-700 diacrylate,2,2-bis[-4-(acryloxydiethoxy)phenyl]propane, triethylene glycoldiacrylate, tripropylene glycol diacrylate, SR 349 (Sartomer),polyethylene glycol-600 diacrylate, and propoxylated neopentyl glycoldiacrylate.

A suitable example of an unsubstituted oligo(meth)acrylate istrimethylolpropane triacrylate.

Suitable examples of substituted oligo(meth)acrylates are: M-325(Siber-Hegner), dipentacrythritol pentaacrylate and hexaacrylate, A-TMMT(Siber-Hegner), tetramethylolmethane triacrylate, trimethylolmethanoltriacrylate, trimethylolpropane ethoxylate triacrylate,tris(acryloyloxyethyl) phosphate, tris(2-hydroxyethyl)isocyanuratetriacrylate, ethoxylated trimethylolpropane triacrylate, propoxylatedtrimethylolpropane triacrylate, propoxylated glyceryl triacrylate,di(trimethylolpropane) tetraacrylate, di(pentaerythritol) pentaacrylate,pentaerythritol triacrylate, and ethoxylated pentaerythritoltetraacrylate.

Suitable examples of unsubstituted mono(meth)acrylates are methylacrylate, ethyl acrylate, butyl acrylate, methyl methacrylate,cyclohexyl acrylate, isobornyl acrylate, lauryl acrylate, stearylacrylate, ethylhexyl acrylate, tridecyl acrylate, isooctyl acrylate.

Suitable examples of substituted mono(meth)acrylates or relatedcompounds are: perfluoroalkylethyl acrylate (Fluowet AC 812, HoechstAG), 2-acrylamido-2-methyl-1-propanesulfonic acid (Lubrizol),2-acryloyloxyethyl hydrogen phthalate (Viscoat 2000, Siber-Hegner GmbH),beta-acryloyloxyethyl hydrogen succinate (ASA, Siber-hegner GmbH),acryloyloxyethylphosphoric acid (Lightester Pa., Toagosei),2-acryloyloxypropyl hydrogen phthalate (Viscoat 2100, Siber-HegnerGmbH), the potassium salt of (3-sulfopropyl) acrylate, the dipotassiumsalt of bis(3-sulfopropyl) itaconate,N,N-dimethyl-N-methacryloxaethyl-N-(3-sulfopropyl)ammonium betaine,2-carboxyethyl acrylate, 2-hydroxyethyl acrylate, 2-ethylthioethylmethacrylate, acrylamide, methyl 2-acrylamido-2-methoxyacetate,acrylonitrile, (2-(acryl-oxy)ethyl)(4-benzenebenzyl)dimethylammoniumbromide, (2-hydroxyethyl) acrylate, acryloxydimethylbutyrolactone,acrylic acid, methoxypolyethylene glycol-400 acrylate, nonylphenolethoxylate acrylate (N-117E, Siber-Hegner), nonylphenol diethoxylateacrylate, phenoxydiethylene glycol acrylate, phenoxyethyl acrylate,dimethylaminoethyl acrylate, methyl chloride salt of dimethylaminoethylacrylate, glycidyl acrylate, phenoxypolyethylene glycol acrylate,2,2,3,3-tetrafluoropropyl acrylate, methoxypolyethylene glycol-1000methacrylate, tetrahydrofurfuryl acrylate, caprolactone acrylate,2(2-ethoxyethoxy)ethyl acrylate, 2-acrylamidoglycolic acid.

The molar ratio of the non-resin crosslinking agent to the liquid aminosilicone compound is from about 0.05:1 to about 10:1, preferably fromabout 0.1:1 to about 5:1, more preferably from about 0.5:1 to about 3:1.

Silicone Resin

Typically, the amino silicone nanoemulsion of the present disclosure issubstantially free of a silicone resin.

An example of a silicone resin is a mixture ofpolyorganosiloxane-silicone resins, where each of the one or moresilicone resins of the polyorganosiloxane-silicone resin mixturecontains at least about 80 mol % of units selected from the groupconsisting of units of the general formulas 3, 4, 5, 6:

R⁴ ₃SiO_(1/2)  (3),

R⁴ ₂SiO_(2/2)  (4),

R⁴SiO_(3/2)  (5),

SiO_(4/2)  (6),

in which R⁴ is selected from H, —OR, or —OH residues or monovalenthydrocarbon residues with 1 to 40 carbon atoms, optionally substitutedwith halogens, where at least 20 mol % of the units are selected fromthe group consisting of units of the general formulas 5 and 6, and amaximum of 10 wt % of the R⁴ residues are —OR and —OH residues.

Solvent

The amino silicone nanoemulsion of the present invention comprises fromabout 0.1% to about 50% of one or more solvents, by weight of the aminosilicone. The amino silicone nanoemulsion may comprise from about 0.1%to about 40% of one or more solvents, by weight of the amino silicone.The amino silicone nanoemulsion may comprise from about 1% to about 30%,or about 1% to about 25%, or about 1% to about 20% of one or moresolvents, by weight of the amino silicone. The amino siliconenanoemulsion may comprise from about 1% to about 15% or from about 2% toabout 10% of one or more solvents, by weight of the amino silicone. Theamino silicone nanoemulsion may comprise from about 0.1% to about 5% ofone or more solvents, by weight of the amino silicone. The aminosilicone nanoemulsion may comprise from about 1% to about 5% or fromabout 2% to about 5% of one or more solvents, by weight of the aminosilicone.

The solvent is selected from monoalcohols, polyalcohols, ethers ofmonoalcohols, ethers of polyalcohols, or mixtures thereof. Typically,the solvent has a hydrophilic-lipophilic balance (HLB) ranging fromabout 6 to about 14. More typically, the HLB of the solvent will rangefrom about 8 to about 12, most typically about 11. One type of solventmay be used alone or two or more types of solvents may be used together.

The solvent may comprise a glycol ether, an alkyl ether, an alcohol, analdehyde, a ketone, an ester, or a mixture thereof.

The solvent may be selected from a monoethylene glycol monoalkyl etherthat comprises an alkyl group having 4-12 carbon atoms, a diethyleneglycol monoalkyl ether that comprises an alkyl group having 4-12 carbonatoms, or a mixture thereof. Suitable alkyl groups include butyl groups,hexyl groups, heptyl groups, octyl groups, 2-ethylhexyl groups, nonylgroups, decyl groups, undecyl groups, and dodecyl groups. The alkylgroup may be a hexyl group, e.g., diethylene glycol monohexyl ether orethylene glycol monohexyl ether.

Suitable examples of monoethylene glycol monoalkyl ethers and diethyleneglycol monoalkyl ethers include ethylene glycol monobutyl ether,ethylene glycol monohexyl ether, ethylene glycol monooctyl ether,ethylene glycol monodecyl ether, and ethylene glycol monododecyletherdiethylene glycol monobutyl ether, diethylene glycol monohexylether, diethylene glycol monooctyl ether, diethylene glycol monodecylether, and diethylene glycol monododecyl ether. The solvent may beethylene glycol monohexyl ether, diethylene glycol monohexyl ether, or amixture thereof.

The solvent may comprise an ethylene glycol monoalkyl ether thatcomprises an alkyl group having 4-12 carbon atoms, a diethylene glycolmonoalkyl ether that comprises an alkyl group having 4-12 carbon atoms,an ethylene glycol monohexyl ether, an ethylene glycol monobutyl ether,a diethylene glycol monohexyl ether, a diethylene glycol monobutylether, or combinations thereof.

Surfactant

The amino silicone nanoemulsion of the present invention comprises fromabout 1% to about 50% of one or more surfactants, by weight of the aminosilicone. The amino silicone nanoemulsion may comprise from about 1% toabout 40%, or from about 1% to about 30%, or from about 1% to about 25%,or from about 1% to about 20% of one or more surfactants, by weight ofthe amino silicone. The amino silicone nanoemulsion may comprise fromabout 5% to about 20% or from about 10% to about 20% of one or moresurfactants, by weight of the amino silicone. The surfactant is selectedfrom anionic surfactants, nonionic surfactants, cationic surfactants,zwitterionic surfactants, amphoteric surfactants, ampholyticsurfactants, or mixtures thereof. The amino silicone nanoemulsion of thepresent disclosure may comprise a nonionic surfactant, a cationicsurfactant, or a mixture thereof. The amino silicone nanoemulsion of thepresent disclosure may comprise a nonionic surfactant. It is believedthat surfactant facilitates uniform dispersing of the amino siliconefluid compound and the solvent in water.

Nonionic Surfactants

Suitable nonionic surfactants useful herein may comprise anyconventional nonionic surfactant. More specific examples of suitablenonionic surfactants include, for example, polyoxyethylene alkyl ethers,polyoxyethylene polyoxypropylene alkyl ethers or other polyoxyalkylenealkyl ethers; polyoxyethylene alkylphenyl ethers; polyoxyethylene alkylesters; polyoxyethylene alkyl phenyl ether sorbitan esters; glycerinesters; sorbitan fatty acid esters; sucrose fatty acid esters or otherpolyhydric alcohol fatty acid esters; ethoxylated fatty acids; andethoxylated fatty acid amides. The nonionic surfactant may be selectedfrom polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylenealkyl ethers, or a mixture thereof. Typically, total HLB(hydrophilic-lipophilic balance) of the nonionic surfactant that is usedis in the range of about 8-16, more typically in the range of 10-15.

Other non-limiting examples of nonionic surfactants useful hereininclude alkoxylated fatty alcohols, e.g., ethoxylated nonionicsurfactant, and amine oxide surfactants. These materials are describedin U.S. Pat. No. 4,285,841, Barrat et al, issued Aug. 25, 1981. Thenonionic surfactant may be selected from the ethoxylated alcohols andethoxylated alkyl phenols of the formula R(OC₂H₄)_(n)OH, wherein R isselected from the group consisting of aliphatic hydrocarbon radicalscontaining from about 8 to about 15 carbon atoms and alkyl phenylradicals in which the alkyl groups contain from about 8 to about 12carbon atoms, and the average value of n is from about 5 to about 15.These surfactants are more fully described in U.S. Pat. No. 4,284,532,Leikhim et al, issued Aug. 18, 1981. Further non-limiting examples ofnonionic surfactants useful herein include: C₁₂-C₁₈ alkyl ethoxylates,such as, NEODOL® nonionic surfactants from Shell; C₆-C₁₂ alkyl phenolalkoxylates wherein the alkoxylate units are a mixture of ethyleneoxyand propyleneoxy units; C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenolcondensates with ethylene oxide/propylene oxide block polymers such asPluronic® from BASF; C₁₄-C₂₂ mid-chain branched alcohols, BA, asdiscussed in U.S. Pat. No. 6,150,322; C₁₄-C₂₂ mid-chain branched alkylalkoxylates, BAE_(x), wherein x is from 1 to 30, as discussed in U.S.Pat. No. 6,153,577, U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,093,856;Alkylpolysaccharides as discussed in U.S. Pat. No. 4,565,647 to Llenado,issued Jan. 26, 1986; specifically alkylpolyglycosides as discussed inU.S. Pat. No. 4,483,780 and U.S. Pat. No. 4,483,779; Polyhydroxy fattyacid amides as discussed in U.S. Pat. No. 5,332,528, WO 92/06162, WO93/19146, WO 93/19038, and WO 94/09099; and ether cappedpoly(oxyalkylated) alcohol surfactants as discussed in U.S. Pat. No.6,482,994 and WO 01/42408.

Cationic Surfactants

The amino silicone nanoemulsion of the present invention may comprise acationic surfactant. The amino silicone nanoemulsion may comprise fromabout 1% to about 50% of a cationic surfactant, by weight of the aminosilicone. The amino silicone nanoemulsion may comprise from about 1% toabout 40% or from about 1% to about 30% of a cationic surfactant, byweight of the amino silicone. The amino silicone nanoemulsion maycomprise from about 2% to about 20% or from about 2% to about 15% of acationic surfactant, by weight of the amino silicone. The cationicsurfactant may have an HLB of from about 18 to about 25.

Cationic surfactants include, for example, alkyl trimethylammoniumchloride, alkylamine hydrochloric acid salts, alkylamine acetate,alkylbenzene dimethyl ammonium chloride and the like.

Non-limiting examples of cationic surfactants include: the quaternaryammonium surfactants, which can have up to 26 carbon atoms include:alkoxylate quaternary ammonium (AQA) surfactants as discussed in U.S.Pat. No. 6,136,769; dimethyl hydroxyethyl quaternary ammonium asdiscussed in U.S. Pat. No. 6,004,922; dimethyl hydroxyethyl laurylammonium chloride; polyamine cationic surfactants as discussed in WO98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006;cationic ester surfactants as discussed in U.S. Pat. Nos. 4,228,042,4,239,660 4,260,529 and U.S. Pat. No. 6,022,844; and amino surfactantsas discussed in U.S. Pat. No. 6,221,825 and WO 00/47708, specificallyamido propyldimethyl amine (APA).

Anionic Surfactants

Suitable anionic surfactants include sulphate and sulphonatesurfactants. Suitable sulphonate surfactants include alkyl benzenesulphonate, e.g., C₁₀₋₁₃ alkyl benzene sulphonate. Suitable alkylbenzene sulphonate (LAS) may be obtained, by sulphonating commerciallyavailable linear alkyl benzene (LAB); suitable LAB includes low 2-phenylLAB, such as those supplied by Sasol under the tradename Isochem® orthose supplied by Petresa under the tradename Petrelab®, other suitableLAB include high 2-phenyl LAB, such as those supplied by Sasol under thetradename Hyblene®. A suitable anionic surfactant is alkyl benzenesulphonate that is obtained by DETAL catalyzed process, although othersynthesis routes, such as HF, may also be suitable. A magnesium salt ofLAS may be used.

Suitable sulphate surfactants include alkyl sulphate, e.g., C₈₋₁₈ alkylsulphate, or predominantly C₁₂ alkyl sulphate.

Another suitable sulphate surfactant may be alkyl alkoxylated sulphate,for example, alkyl ethoxylated sulphate, such as a C₈₋₁₈ alkylalkoxylated sulphate. Another suitable sulphate surfactant may be aC₈₋₁₈ alkyl ethoxylated sulphate. The alkyl alkoxylated sulphate mayhave an average degree of alkoxylation of from 0.5 to 20, or from 0.5 to10. The alkyl alkoxylated sulphate may be a C₈₋₁₈ alkyl ethoxylatedsulphate having an average degree of ethoxylation of from 0.5 to 10,from 0.5 to 7, from 0.5 to 5 or even from 0.5 to 3.

The alkyl sulphate, alkyl alkoxylated sulphate, and alkyl benzenesulphonates may be linear or branched, substituted or un-substituted.

The surfactant may be a mid-chain branched surfactant, e.g., a mid-chainbranched anionic detersive surfactant, such as a mid-chain branchedalkyl sulphate and/or a mid-chain branched alkyl benzene sulphonate. Themid-chain branches may be C₁₋₄ alkyl groups, typically methyl and/orethyl groups.

Zwitterionic Surfactants

Examples of zwitterionic surfactants include: derivatives of secondaryand tertiary amines, derivatives of heterocyclic secondary and tertiaryamines, or derivatives of quaternary ammonium, quaternary phosphonium ortertiary sulfonium compounds. See U.S. Pat. No. 3,929,678 at column 19,line 38 through column 22, line 48, for examples of zwitterionicsurfactants; betaines, including alkyl dimethyl betaine and cocodimethylamidopropyl betaine, C₈ to C₁₈ (for example from C₁₂ to C₁₈) amineoxides. and sulfo and hydroxy betaines, such asN-alkyl-N,N-dimethylammino-1-propane sulfonate where the alkyl group canbe C₈ to C₁₈ and in certain embodiments from C₁₀ to C₁₄.

Ampholytic Surfactants

Specific, non-limiting examples of ampholytic surfactants include:aliphatic derivatives of secondary or tertiary amines, or aliphaticderivatives of heterocyclic secondary and tertiary amines in which thealiphatic radical can be straight- or branched-chain. One of thealiphatic substituents may contain at least about 8 carbon atoms, forexample from about 8 to about 18 carbon atoms, and at least one containsan anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate.See U.S. Pat. No. 3,929,678 at column 19, lines 18-35, for suitableexamples of ampholytic surfactants.

Amphoteric Surfactants

Amphoteric surfactants include, for example,N-acylamidopropyl-N,N-dimethyl ammonia betaines,N-acylamidopropyl-N,N′-dimethyl-N′-β-hydroxypropyl ammonia betaines, andthe like.

Examples of amphoteric surfactants include: aliphatic derivatives ofsecondary or tertiary amines, or aliphatic derivatives of heterocyclicsecondary and tertiary amines in which the aliphatic radical can bestraight- or branched-chain. One of the aliphatic substituents containsat least about 8 carbon atoms, typically from about 8 to about 18 carbonatoms, and at least one contains an anionic water-solubilizing group,e.g. carboxy, sulfonate, sulfate. Examples of compounds falling withinthis definition are sodium 3-(dodecylamino)propionate, sodium3-(dodecylamino) propane-1-sulfonate, sodium 2-(dodecylamino)ethylsulfate, sodium 2-(dimethylamino) octadecanoate, disodium3-(N-carboxymethyldodecylamino)propane 1-sulfonate, disodiumoctadecyl-imminodiacetate, sodium 1-carboxymethyl-2-undecylimidazole,and sodium N,N-bis (2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine. SeeU.S. Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 atcolumn 19, lines 18-35, for examples of amphoteric surfactants.

Other Surfactants

Polyester modified silicone or other silicone surfactants may also beoptionally used in small amounts, e.g., less than 5%.

Water

The amino silicone nanoemulsion comprises from about 10% to about99.99%, of water, by weight. The amino silicone nanoemulsion may includewater in amounts of from about 10% to about 50%, by weight. In aconcentrated consumer product, such as a laundry detergent or a shampoo,the amino silicone nanoemulsion may include water in amounts of fromabout 20% to about 90%, by weight. In a diluted consumer product beingused as a treatment composition, the amino silicone nanoemulsion mayinclude water in amounts of from about 20% to about 99.99%, by weight.

Protonating Agent

The protonating agent is generally a monoprotic or multiprotic,water-soluble or water-insoluble, organic or inorganic acid. Suitableprotonating agents include, for example, formic acid, acetic acid,propionic acid, malonic acid, citric acid, hydrochloric acid, sulfuricacid, phosphoric acid, nitric acid, or a mixture thereof. Theprotonating agent may be selected from formic acid, acetic acid, or amixture thereof. The protonating agent may be acetic acid. Generally,the acid is added in the form of an acidic aqueous solution.

The protonating agent is added in an amount necessary to achieve ananoemulsion pH of from about 3.5 to about 11.0. The amino siliconenanoemulsions may comprise the protonating agent in an amount necessaryto achieve a pH of from about 3.5 to about 6.5 or about 4.0 to about6.0. The amino silicone nanoemulsinos may comprise the protonating agentin an amount necessary to achieve a pH of from about 5.0 to about 6.0 orabout 5.5. The pH of the amino silicone nanoemulsion may be from about3.5 to about 10.5 or about 4.0 to about 10.0. The pH of the aminosilicone nanoemulsion may be from about 5.0 to about 9.0 or about 6.0 toabout 8.0. The pH of the amino silicone nanoemulsion may be less thanabout 10.5.

Stabilizer

The amino silicone nanoemulsions may also comprise auxiliary stabilizersselected from mono- or polyalcohols and ethers thereof, which have aboiling point or boiling range of at most 260° C. at 0.10 MPa. Examplesof monoalcohols are ethanol, n-propanol, isopropanol and butanol.Examples of polyalcohols are ethylene glycol and propylene glycol.Examples of polyalcohol ethers are ethylene glycol monobutyl ether,ethylene glycol monoethyl ether and diethylene glycol monoethyl ether.If used, the nanoemulsions may include auxiliary stabilizers at levelsup to about 10%. Certain embodiments of the nanoemulsions optionallycomprise from about 1% to about 7%, while others optionally comprisefrom about 2% to about 5% of the auxiliary stabilizer.

Optional Nanoemulsion Adjunct Ingredients

The amino silicone nanoemulsions may additionally include furthersubstances, such as preservatives, scents, corrosion inhibitors anddyes. Examples of preservatives are alcohols, formaldehyde, parabens,benzyl alcohol, propionic acid and salts thereof and alsoisothiazolinones. The nanoemulsions may further include yet otheradditives, such as non-silicon-containing oils and waxes. Examplesthereof are rapeseed oil, olive oil, mineral oil, paraffin oil ornon-silicon-containing waxes, for example carnauba wax and candelillawax or montan acid and montan ester waxes, incipiently oxidizedsynthetic paraffins, polyethylene waxes, polyvinyl ether waxes andmetal-soap-containing waxes. The amino silicone nanoemulsions mayfurther comprise carnauba wax, paraffin wax, polyethylene wax, or amixture thereof. The nanoemulsions may comprise up to about 5% by weightof the nanoemulsion or from about 0.05% to about 2.5% by weight of thenanoemulsion of such further substances.

Treatment Composition

The amino silicone nanoemulsions of the present invention may beincorporated into treatment compositions or cleaning compositions, suchas, but not limited to, a fabric care composition, a dish cleaningcomposition, a home care composition, a beauty care composition, or apersonal care composition. The treatment composition may comprise fromabout 0.001% to about 99% by weight of the composition, of the aminosilicone nanoemulsion. The treatment composition may comprise from about0.001% to about 15% of the amino silicone nanoemulsion, by weight of thecomposition.

Examples of treatment and cleaning compositions include, but are notlimited to, liquid laundry detergents, solid laundry detergents, laundrysoap products, laundry spray treatment products, laundry pre-treatmentproducts, fabric enhancer products, hand dish washing detergents,automatic dishwashing detergents, a beauty care detergent, hard surfacecleaning detergents (hard surfaces include exterior surfaces, such asvinyl siding, windows, and decks), carpet cleaning detergents,conditioners, a shampoo, shave preparation products, and a householdcleaning detergent. Examples of fabric care compositions suitable forthe present disclosure include, but are not limited to, liquid laundrydetergents, heavy duty liquid laundry detergents, solid laundrydetergents, laundry soap products, laundry spray treatment products,laundry pre-treatment products, laundry soak products, heavy duty liquiddetergents, and rinse additives. Examples of suitable dish cleaningcompositions include, but are not limited to, automatic dishwasherdetergents, detergents for hand washing of dishes, liquid dish soap, andsolid granular dish soap. Examples of suitable home care compositionsinclude, but are not limited to, rug or carpet cleaning compositions,hard surface cleaning detergents, floor cleaning compositions, windowcleaning compositions, household cleaning detergents, and car washingdetergents. Examples of suitable personal care compositions include, butare not limited to, beauty care cleansers, such as hair and skincleansers, beauty bars, bar soap, bath beads, bath soaps, hand washingcompositions, body washes and soaps, shampoo, conditioners, cosmetics,hair removal compositions, and oral care compositions.

The treatment composition may be provided in combination with a nonwovensubstrate, as a treatment implement.

The compositions may provide water and/or oil repellency to the treatedsurface, thereby reducing the propensity of the treated surface tobecome stained by deposited water- or oil-based soils.

By “surfaces” it is meant any surface. These surfaces may include porousor non-porous, absorptive or non-absorptive substrates. Surfaces mayinclude, but are not limited to, celluloses, paper, natural and/orsynthetic textiles fibers and fabrics, imitation leather and leather,hair and skin. The present invention may be applied to natural and/orsynthetic textile fibers and fabrics.

By “treating a surface” it is meant the application of the compositiononto the surface. The application may be performed directly, such asspraying or wiping the composition onto a hard surface. The compositionmay or may not be rinsed off, depending on the desired benefit.

The present invention also encompasses the treatment of a fabric as thesurface. This can be done either in a “pretreatment mode”, where thecomposition is applied neat onto the fabric before the fabrics arewashed or rinsed, or a “post-treatment mode”, where the composition isapplied neat onto the fabric after the fabric is washed or rinsed. Thetreatment may be performed in a “soaking mode”, where the fabric isimmersed and soaked in a bath of neat or diluted composition. Thetreatment may also be performed in a “through the wash” or “through therinse” mode where the treatment composition, as defined herein, is addedto the wash cycle or the rinse cycle of a typical laundry wash machinecycle. When used in the wash or rinse cycle, the compositions aretypically used in a diluted form. By “diluted form” it is meant that thecompositions may be diluted in the use, preferably with water at a ratioof water to composition up to 500:1, or from 5:1 to 200:1, or from 10:1to 80:1.

Such treatment compositions may comprise carriers, which may be anyknown material that is useful in delivering the treatment compositionsto the surface to be treated. The carrier may be as simple as a singlecomponent delivery vehicle, such as water or alcohol, which would allowthe nanoemulsion to be sprayed onto a surface. Alternatively, thecarrier may be complex, such as a cleaning composition, e.g., a laundrydetergent where the nanoemulsion would be applied in conjunction withthe other beneficial uses of the complex carrier.

Such treatment compositions may comprise various other materials,including bleaching agents, bleach activators, detersive surfactants,builders, chelating agents, smectite clays, dye transfer inhibitingagents, dispersants, enzymes, and enzyme stabilizers, catalytic metalcomplexes, polymeric dispersing agents, clay and soilremoval/anti-redeposition agents, brighteners, suds suppressors, sudsboosters, dyes, additional perfumes and perfume delivery systems,structure elasticizing agents, fabric softeners, carriers, hydrotropes,processing aids and/or pigments.

Detersive Surfactants—The treatment compositions according to thepresent disclosure may comprise a detersive surfactant or detersivesurfactant system. Suitable detersive surfactants include nonionicsurfactant, anionic surfactant, cationic surfactant, ampholyticsurfactant, zwitterionic surfactant, semi-polar nonionic surfactant, ora mixture thereof. The detersive surfactant is typically present at alevel of from about 0.1%, from about 1%, or even from about 5%, byweight of the treatment composition, to about 99.9%, to about 80%, toabout 35%, or even to about 30%, by weight of the treatment composition.The specific surfactants described above, in the context of thenanoemulsion itself, may be included in the treatment compositions asdetersive surfactants. When included in the treatment compositions (asopposed to the nanoemulsion itself), these surfactants are generallyincluded at appropriate concentrations such that the surfactants providea detersive or cleaning benefit.

Builders—The treatment compositions of the present disclosure maycomprise one or more detergent builders or builder systems. Whenpresent, the compositions will typically comprise at least about 1%builder, or from about 5% or 10% to about 80%, 50%, or even 30% byweight, of said builder. Builders include, but are not limited to, thealkali metal, ammonium and alkanolammonium salts of polyphosphates,alkali metal silicates, alkaline earth and alkali metal carbonates,aluminosilicate builders polycarboxylate compounds, etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, andcarboxymethyl-oxysuccinic acid, the various alkali metal, ammonium andsubstituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylatessuch as mellitic acid, succinic acid, oxydisuccinic acid, polymaleicacid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid,and soluble salts thereof.

Chelating Agents—The treatment compositions may also optionally containone or more copper, iron and/or manganese chelating agents. If utilized,chelating agents will generally comprise from about 0.1% by weight ofthe compositions herein to about 15%, or even from about 3.0% to about15% by weight of the compositions herein.

Dye Transfer Inhibiting Agents—The treatment compositions of the presentdisclosure may also include one or more dye transfer inhibiting agents.Suitable polymeric dye transfer inhibiting agents include, but are notlimited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers,copolymers of N-vinylpyrrolidone and N-vinylimidazole (PVPVI),polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Whenpresent in the compositions herein, the dye transfer inhibiting agentsare present at levels from about 0.0001%, from about 0.01%, from about0.05% by weight of the cleaning compositions to about 10%, about 2%, oreven about 1% by weight of the cleaning compositions.

Dispersants—The treatment compositions of the present disclosure mayalso contain dispersants. Suitable water-soluble organic materials arethe homo- or co-polymeric acids or their salts, in which thepolycarboxylic acid may comprise at least two carboxyl radicalsseparated from each other by not more than two carbon atoms.

Enzymes—The treatment compositions may comprise one or more detergentenzymes, which provide cleaning performance and/or fabric care benefits.Examples of suitable enzymes include, but are not limited to,hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases,phospholipases, esterases, cutinases, pectinases, keratanases,reductases, oxidases, phenoloxidases, lipoxygenases, ligninases,pullulanases, tannases, pentosanases, malanases, β-glucanases,arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, ormixtures thereof. A typical combination is a cocktail of conventionalapplicable enzymes like protease, lipase, cutinase and/or cellulase inconjunction with amylase.

Enzyme Stabilizers—Enzymes for use in the treatment compositions, e.g.,detergents, may be stabilized by various techniques. The enzymesemployed herein can be stabilized by the presence of water-solublesources of calcium and/or magnesium ions in the finished compositionsthat provide such ions to the enzymes.

The treatment composition may comprise an amino silicone nanoemulsionand a carrier. Typically, the amino silicone nanoemulsion issubstantially free of a silicone resin. The treatment composition maycomprise an amino silicone nanoemulsion, a carrier, and a perfume, adetersive surfactant system, or a cleaning adjunct additive. Thedetersive surfactant system may comprise one or more surfactantsselected from nonionic surfactants, cationic surfactants, anionicsurfactants, zwitterionic surfactants, ampholytic surfactants, oramphoteric surfactants. The detersive surfactant system may comprise asurfactant selected from C₁₀-C₁₆ alkyl benzene sulfonates, C₈-C₁₈ alkylsulfate, C₈-C₁₈ alkyl ethoxylated sulfate, or a mixture thereof.

The treatment composition may be a fabric care composition. Such afabric care composition may take the form of detergent composition or arinse added fabric conditioning compositions. Such compositions maycomprise a fabric softening active and a dispersant polymer, to providea stain repellency benefit to fabrics treated by the composition,typically from about 0.00001 wt. % (0.1 ppm) to about 1 wt. % (10,000ppm), or even from about 0.0003 wt. % (3 ppm) to about 0.03 wt. % (300ppm) based on total rinse added fabric conditioning composition weight.The compositions may be rinse added fabric conditioning compositions.Examples of typical rinse added conditioning composition can be found inU.S. Provisional Patent Application Ser. No. 60/687,582 filed on Oct. 8,2004.

The treatment composition may be encapsulated in a water-soluble orwater-dispersible pouch. The water-soluble film or pouch may comprisepolyvinyl alcohol, polyvinyl acetate, or mixtures thereof. The unit doseform may comprise at least two compartments, or at least threecompartments. At least one compartment may be superimposed on anothercompartment.

The treatment composition may be in the form of a granule. Granulartreatment compositions may include any number of conventional detergentingredients, such as the components described above, e.g., surfactants,chelants, enzymes. Granular detergent compositions typically comprisefrom about 1% to 95% by weight of a surfactant. Granular detergents canbe made by a wide variety of processes, non-limiting examples of whichinclude spray drying, agglomeration, fluid bed granulation,marumarisation, extrusion, or a combination thereof. Bulk densities ofgranular detergents generally range from about 300 g/l-1000 g/l. Theaverage particle size distribution of granular detergents generallyranges from about 250 microns-1400 microns.

The treatment composition disclosed herein may be selected from a beautycare composition, a hand washing composition, a body wash composition, ashampoo composition, a conditioner composition, a cosmetic composition,a hair removal composition, a oral care composition, a laundry spraycomposition, a laundry rinse additive composition, a liquid laundrydetergent compositions, a solid laundry detergent compositions, a hardsurface cleaning compositions, a liquid hand dishwashing compositions, asolid automatic dishwashing compositions, a liquid automaticdishwashing, and a tab/unit dose form automatic dishwashingcompositions, and a laundry detergent compositions contained in awater-soluble pouch.

Method of Making Treatment Composition Comprising Amino SiliconeNanoemulsion

The treatment compositions disclosed herein may be prepared by combiningthe components thereof in any convenient order and by mixing, e.g.,agitating, the resulting component combination to form a phase stablecleaning composition. A liquid matrix may be formed containing at leasta major proportion, or even substantially all, of the liquid components,e.g., nonionic surfactant, the non-surface active liquid carriers andother optional liquid components, with the liquid components beingthoroughly admixed by imparting shear agitation to this liquidcombination. For example, rapid stirring with a mechanical stirrer mayusefully be employed. While shear agitation is maintained, substantiallyall of any anionic surfactant and the solid ingredients can be added.Agitation of the mixture is continued, and if necessary, can beincreased at this point to form a solution or a uniform dispersion ofinsoluble solid phase particulates within the liquid phase. After someor all of the solid-form materials have been added to this agitatedmixture, particles of any enzyme material to be included, e.g., enzymeprills are incorporated. As a variation of the composition preparationprocedure described above, one or more of the solid components may beadded to the agitated mixture as a solution or slurry of particlespremixed with a minor portion of one or more of the liquid components.After addition of all of the composition components, agitation of themixture is continued for a period of time sufficient to formcompositions having the requisite viscosity and phase stabilitycharacteristics. Frequently this will involve agitation for a period offrom about 30 to 60 minutes.

The amino silicone nanoemulsion may first be combined with one or moreliquid components to form an aqueous amino silicone nanoemulsion premix,and this aqueous amino silicone nanoemulsion premix is added to acomposition formulation containing a substantial portion, for examplemore than 50% by weight, more than 70% by weight, or even more than 90%by weight, of the balance of components of the cleaning composition. Forexample, in the methodology described above, both the aqueous aminosilicone nanoemulsion premix and the enzyme component are added at afinal stage of component additions. The aqueous amino siliconenanoemulsion may be encapsulated prior to addition to the detergentcomposition, the encapsulated aqueous amino silicone nanoemulsion issuspended in a structured liquid, and the suspension is added to acomposition formulation containing a substantial portion of the balanceof components of the cleaning composition.

Methods of Using Treatment Compositions

The treatment compositions of the present disclosure may be used in amethod of treating a surface. The method of treating a surface comprisesthe step of applying the amino silicone nanoemulsion treatmentcomposition of the present disclosure to a surface, where the surface isselected from fabric, skin, hair, or a hard surface.

Fabric Treatment

The treatment compositions disclosed in the present specification may beused to clean or treat a fabric, such as those described herein.Typically at least a portion of the fabric is contacted with anembodiment of the aforementioned fabric care compositions, in neat formor diluted in a liquor, for example, a wash liquor and then the fabricmay be optionally washed and/or rinsed and/or dried without furthertreatment. A fabric may be optionally washed and/or rinsed, contactedwith an embodiment of the aforementioned fabric care compositions andthen optionally washed and/or rinsed. For purposes of the presentdisclosure, washing includes but is not limited to, scrubbing, andmechanical agitation. The fabric may comprise most any fabric capable ofbeing laundered or treated.

The fabric care compositions disclosed in the present specification canbe used to form aqueous washing or treatment solutions for use in thelaundering and/or treatment of fabrics. Generally, an effective amountof such compositions is added to water, preferably in a conventionalfabric laundering automatic washing machine, to form such aqueouslaundering solutions. The aqueous washing solution so formed is thencontacted, preferably under agitation, with the fabrics to be launderedtherewith. An effective amount of the fabric care composition, such asthe liquid detergent compositions disclosed in the presentspecification, may be added to water to form aqueous launderingsolutions that may comprise from about 500 to about 7,000 ppm or evenfrom about 1,000 to about 3,000 ppm of fabric care composition.

The fabric care compositions may be employed as a laundry additive, apre-treatment composition and/or a post-treatment composition.

Without being bound by theory it is believed the treatment of a fabricwith compositions disclosed in the present specification may increasethe time-to-wick of the fabric. Table 1 shows an increase in thetime-to-wick of cotton fabric as a result of treatment with examples ofcompositions disclosed in the present specification.

There is provided a method of treating a surface comprising the step ofapplying the amino silicone nanoemulsion treatment composition of thepresent disclosure to a surface, where the surface is a fabric and wherethe water repellency relative to the untreated fabric is increased, asmeasured by an increase in Time to Wick. The increase in Time to Wickmay be greater than about 100 seconds, or greater than about 500seconds, or greater than about 1200 seconds. The oil repellency relativeto the untreated fabric may be increased, as measured by an increase inTime to Wick. The oil repellency relative to the untreated fabric may beincreased, as measured by an increase in Time to Wick greater than about10 seconds.

Hair Treatment

The treatment compositions disclosed in the present specification may beused to clean or treat hair. Typically at least a portion of the hair iscontacted with an embodiment of the aforementioned hair carecompositions, in neat form or diluted in a liquor, for example, a washliquor, and then the hair may be optionally washed and/or rinsed and/ordried without further treatment. Hair may be optionally washed and/orrinsed, contacted with an embodiment of the aforementioned hair carecompositions and then optionally washed and/or rinsed and/or driedwithout further treatment. For purposes of the present disclosure,washing includes but is not limited to, scrubbing, and mechanicalagitation.

The hair care compositions disclosed in the present specification can beused to form aqueous washing or treatment solutions for use in thewashing and/or treatment of hair. Generally, an effective amount of suchcompositions is added to water to form such aqueous washing and/ortreatment solutions. The aqueous washing and/or treatment solution soformed is then contacted with the hair to be washed or treatedtherewith.

Without being bound by theory, it is believed the treatment of the hairwith compositions disclosed in the present specification may decreasethe dry-time of the hair after treatment. For example if the treatmentwere a hair-conditioning treatment applied in the shower, the timerequired for the hair to dry after such treatment would be reduced byvirtue of the treatment, relative to the time required for the hair todry if there had been no such treatment. Table 2 shows a decrease in thedry-time of hair as a result of treatment with examples of compositionsdisclosed in the present specification.

There is also provided a method of treating a surface comprising thestep of applying the amino silicone nanoemulsion treatment compositionof the present disclosure to a surface, where the surface is hair orskin and where the dry time relative to the untreated hair or skin isdecreased, as measured by an decrease in Technical Dry Time. TheTechnical Dry Time may be less than about 3 seconds.

Hard Surfaces

The treatment compositions disclosed in the present specification may beused to clean or treat hard surfaces, such as those described herein.Typically at least a portion of the hard surface is contacted with anembodiment of the aforementioned hard surface care compositions, in neatform or diluted in a liquor, for example, a wash liquor and then thehard surface may be optionally washed and/or rinsed and/or dried withoutfurther treatment. A hard surface may be optionally washed and/orrinsed, contacted with an embodiment of the aforementioned hard surfacecare compositions and then optionally washed and/or rinsed and/or driedwithout further treatment. For purposes of the present disclosure,washing includes but is not limited to, scrubbing, and mechanicalagitation.

The hard surface care compositions disclosed in the presentspecification can be used to form aqueous washing or treatment solutionsfor use in the washing and/or treatment of hard surfaces. Generally, aneffective amount of such compositions is added to water to form suchaqueous washing and/or treatment solutions. The aqueous washing and/ortreatment solution so formed is then contacted with the hard surface tobe washed or treated therewith.

Without being bound by theory, it is believed the treatment of the hardsurface with compositions disclosed in the present specification mayincrease the contact angle of water or water-based composition and/oroily substances on the hard surface. Without being bound by theory it isbelieved that increasing the contact angle of substances on a hardsurface increases the ease of removing said substances from the surface.Table 3 shows an increase in the contact angle of a silica wafer as aresult of treatment with examples of compositions disclosed in thepresent specification.

There is also provided a method of treating a surface comprising thestep of applying the amino silicone nanoemulsion treatment compositionof the present disclosure to a surface, where the surface is a hardsurface and where the contact angle relative to the untreated hardsurface is increased. The contact angle may be greater than about 36degrees.

While various specific embodiments have been described in detail herein,the present disclosure is intended to cover various differentcombinations of the disclosed embodiments and is not limited to thosespecific embodiments described herein. The various embodiments of thepresent disclosure may be better understood, when read in conjunctionwith the following representative examples. The following representativeexamples are included for purposes of illustration and not limitation.

Examples

For the sake of brevity, the present invention will be shown anddescribed herein primarily by way of reference to obtaining the emulsionfrom a single reactor and dividing the obtained emulsion into multipleportions, however, it will be recognized that such teachings areintended to encompass and are equally applicable to obtaining the first,second, or multiple portions from a plurality of reactors or a pluralityof emulsion batches obtained from a single reactor.

Nanoemulsion Preparations

1) Preparation of Amino Silicone Emulsions with Non-Resin Crosslinker

In a 36 oz jar, 102.0 g of amino silicone fluid (Mn=34527 g/mol, pendentgroup —(CH₂)₃NH(CH₂)₂NH₂ [corresponds to A], m/n=49, 71 mol % SiMe₃ endgroups, 29 mol % SiOH/SiOMe end groups, obtainable from Shin-EtsuSilicones of America, Inc) are premixed with 12.0 g of Diethylene glycolmonohexyl ether (obtainable from Sigma-Aldrich Chemie GmbH) using IKARW20 Digital Dual—Range Mixer at 500 rpm for 30 minutes in a 50° C. oilbath. 8.4 g of Tergitol 15-s-5 and 12.0 g of Tergitol 15-s-12(obtainable from Sigma-Aldrich Chemie GmbH) are added to the jar andmixed at 500 rpm at room temperature for 20 minutes. 463.8 g of DI waterare added to the jar in two steps (309.2 g of DI water is added in thefirst step and 154.6 g of DI water is added in the second step) andmixed at 500 rpm at room temperature for total of 40 minutes. 1.74 ml ofglacial acetic acid (obtainable from VWR International) are added toadjust pH to about 5.5. About 600 g of a 17% amino siliconenanoemulsions are prepared. The average particle size is 35 nm. 29.4 gof the nanoemulsions that contain 5 g of amino silicone are added toeach individual reactor. The amount of the crosslinkers specified in thetable below is then added to the reactor. The reactors are sealed andmixed for 16 hours at room temperature (20° C.-25° C.). After 16 hoursof mixing the reactors are heated to 50° C. and held at 50° C. for anadditional 25 hours.

Alternatively, as stated above, rather than dividing a single emulsionbatch into multiple portions, the multiple portions may be obtained fromseparate reactors or separate emulsion batches from the same reactor.

TABLE 1 Molar Ratio of Amino Crosslinker/ Silicone Crosslinker AminoEmulsions (grams) (grams) Crosslinker Silicone 1 5 0 0 0 2 5 0.186 DBH0.5 3 5 0.371 DBH 1 4 5 0.650 DBH 1.75 5 5 1.114 DBH 3 6 5 0.030 DVA 1 75 0.045 DVA 1.5 8 5 0.090 DVA 3 9 5 0.031 BDDE 1 10  5 0.077 BDDE 2.511* 5 0.026 DMA 1 12* 5 0.066 DMA 2.5 13  5 0.026 HDDA 0.75 14  5 0.034HDDA 1 15  5 0.086 HDDA 2.5  16** 5 0.0190 DCB 1  17** 5 0.0475 DCB 2.5*Added Hydrochloric Acid 10% greater than the amount of amines beingreacted for the crosslinking. **The emulsion was further heated at 85°C. for 72 hours. Dibromohexane (DBH), 1,4-dichloro-2-butene (DCB),butanediol diepoxide (BDDE), dimethyl adipate (DMA), hexane dioldiacrylate (HDDA) (all available from Sigma-Aldrich, Milwaukee, WI).Di-Vinyl Adipate (DVA) (available from Polysciences, Inc., Warrington,PA).2) Preparation of Amino Silicone Emulsions with Non-Resin Crosslinker

In each individual reactor, 5 g of the same amino silicone fluid used inexample 1 is premixed with 0.6 g of Diethylene glycol monohexyl etherusing IKA RW20 Digital Dual—Range Mixer at 500 rpm for 30 minutes in a50° C. oil bath. 0.4 g of Tergitol 15-s-5 and 0.6 g of Tergitol 15-s-12are added to the reactor and mixed at 500 rpm at room temperature for 20minutes. 22.7 g of DI water are added to the reactor in two steps (15.1g of DI water is added in the first step and 7.6 g of DI water is addedin the second step) and mixed at 500 rpm at room temperature for totalof 40 minutes. The amount of the crosslinkers specified in the tablebelow is then added to the reactor. The reactors are sealed and mixedfor 16 hours at room temperature (20° C.-25° C.). After 16 hours ofmixing the reactors are heated to 50° C. and held at 50° C. for anadditional 25 hours. 1.74 ml of glacial acetic acid are added to adjustpH to about 5.5. About 29.4 g of a 17% amino silicone nanoemulsions areprepared. The average particle size is 60 to 250 nm.

TABLE 2 Molar Ratio of Amino Crosslinker/ Silicone Crosslinker AminoEmulsions (grams) (grams) Crosslinker Silicone 18 5 0.186 DBH 0.5 19 50.371 DBH 1 20 5 0.650 DBH 1.75 21 5 1.114 DBH 3 22 5 0.030 DVA 1 23 50.045 DVA 1.5 24 5 0.090 DVA 3 25 5 0.031 BDDE 1 26 5 0.077 BDDE 2.5 27* 5 0.026 DMA 1  28* 5 0.066 DMA 2.5 29 5 0.026 HDDA 0.75 30 5 0.034HDDA 1 31 5 0.086 HDDA 2.5  32** 5 0.0190 DCB 1  33** 5 0.0475 DCB 2.5*Added Hydrochloric Acid 10% greater than the amount of amines beingreacted for the crosslinking. **The emulsion was further heated at 85°C. for 72 hours. Dibromohexane (DBH), 1,4-dichloro-2-butene (DCB),butanediol diepoxide (BDDE), dimethyl adipate (DMA), hexane dioldiacrylate (HDDA) (all available from Sigma-Aldrich, Milwaukee, WI).Di-Vinyl Adipate (DVA) (available from Polysciences, Inc., Warrington,PA).3) Preparation of Amino Silicone Emulsions with Non-Resin Crosslinker

In a 6 oz jar, 17.0 g of amino silicone fluid (Mn=34527 g/mol, pendentgroup —(CH₂)₃NH(CH₂)₂NH₂ [corresponds to A], m/n=49, 71 mol % SiMe₃ endgroups, 29 mol % SiOH/SiOMe end groups, obtainable from Shin-EtsuSilicones of America, Inc) are premixed with 0.8 g of Di-Ethylene GlycolmonoHexyl Ether (DEGHE, obtainable from Sigma-Aldrich Chemie GmbH) usingIKA RW20 Digital Dual—Range Mixer at 500 rpm for 30 minutes in a 50° C.oil bath. 3.4 g of DiMethyl Bis (2-Steroyl Oxyethyl) Ammonium Chloride(DMBSOAC) (available from Evonik Degussa Corporation, Parsippany, N.J.,US) are added to the jar and mixed at 500 rpm at room temperature for 20minutes. 78.5 g of De-Ionized (DI) water are added to the jar in twosteps (52.3 g of DI water is added in the first step and 26.2 g of DIwater is added in the second step) and mixed at 500 rpm at roomtemperature for total of 40 minutes. Glacial acetic acid (obtainablefrom VWR International) is added to adjust pH to 5.5. About 100 g of a17% amino silicone nanoemulsion is prepared. The average particle sizeis 125 nm. 29.4 g of the nanoemulsions that contain 5 g of aminosilicone are added to each individual reactor. The amount of thecrosslinkers specified in the table below is then added to the reactor.The reactors are sealed and mixed for 16 hours at room temperature (20°C.-25° C.). After 16 hours of mixing the reactors are heated to 50° C.and held at 50° C. for an additional 25 hours.

TABLE 3 Molar Ratio of Amino Crosslinker/ Silicone Crosslinker AminoEmulsions (grams) (grams) Crosslinker Silicone 34 5 0 0 0 35 5 0.030 DVA1 36 5 0.371 DBH 1 Di-Vinyl Adipate (DVA) (available from Polysciences,Inc., Warrington, PA). Di-BromoHexane (DBH) (all available fromSigma-Aldrich, Milwaukee, WI).

4) The emulsions in Table 4 were prepared by combining emulsions withoutcrosslinker, nil-crosslinker (A), and corresponding emulsions withcrosslinker (B), chosen from the emulsions shown in Tables 1-3, at roomtemperature.

TABLE 4 Emulsion A (nil- Emulsion B Weight Ratio Emulsions crosslinker)(crosslinker) Crosslinker of A/B 37 Emulsion 1 Emulsion 6 DVA 12:1  386:1 39 3:1 41 Emulsion 34 Emulsion 36 DBH 6:1 Di-Vinyl Adipate (DVA)(available from Polysciences, Inc., Warrington, PA). Di-BromoHexane(DBH) (all available from Sigma-Aldrich, Milwaukee, WI).

Application Examples Fabric Care Application:

Each of the nanoemulsions in Table 5 and Table 6 is diluted to make atreatment composition, in which the concentration of aminosilicone iseither 100 ppm or 50 ppm, using DI water. Cotton fabric CW120(obtainable from Empirical Manufacturing Company, Cincinnati, Ohio) isdipped in the solution and then dried at 60° C. for an hour in an oven.The Time to Wick (T2W) is measured on the fabrics according to the T2Wtesting method. Results are summarized in Tables 5 and 6 below.

Hair Care Application:

Each of the nanoemulsions in Table 5 is diluted to make a treatmentcomposition, in which the concentration of aminosilicone is 10,000 ppm,using DI water. Hair Switches (obtainable from International HairImports & Products, New York) are dipped in the solution and the dryingtime is measured on the hair switches according to the Hair Drying Timetest method. Results are summarized in the Table 5 below.

Hard Surface Application:

Each of the nanoemulsions in Table 5 is diluted to make a treatmentcomposition, in which the concentration of aminosilicone is 500 ppm,using DI water. Solutions are dropped on Silica Wafers (obtainable fromSilicon Valley Microelectronic, Inc, CA) then dried at room temperaturefor 24 hours. Contact angles are measured on the silica wafers accordingto the contact angle test method. Results are summarized in the Table 5below.

TABLE 5 Emulsions 1 6 37 38 39 40* Particle Size (nm) 40 40 40 40 40Water T2W  50 ppm 390 1800 2000 2600 1800 (seconds) 100 ppm3100 >3600 >3600 >3600 >3600 Oil T2W 100 ppm 17 20 20 19 19 (seconds)Drying Time 10,000 ppm   2.7 2.2 2.2 2.2 2.2 3.5 (minutes) Contact ***500 ppm 93 97 97 97 96 Angle (°) *Herbal Essences Drama Clean Shampoo(Lot#: 11225395LF). **Contact Angle on non coated Silica wafer was 36°.

TABLE 6 Emulsions 34 36 41 Water T2W  50 ppm 200 50 350 (seconds) 100ppm 740 1130 2430 Particle Size (nm) 125 150 135 pH 5.5 5.5 5.5

Examples of Treatment and Cleaning Compositions

Liquid laundry additive compositions 1-3 shown below have detailedpercentages based on 100% active basis.

TABLE 7 Ingredient 1 2 3 Dosage 30 g 30 g 30 g emulsions 37-41 6.00%6.00% 12.00% cationic starch¹ 1.20% 1.20% 1.20% TAE80² 0.25% 0.25% 0.25%Antimicrobial³ 0.02% 0.02% 0.02% Perfume 0.40% 0.40% 0.40% ButylCarbitol 3.00% 3.00% 2.00% Polyamine N- 0.00% 0.83% 3.34% oxide ¹Akzo,EXP 5617-2301-28, available from Akzo Nobel. ²Tallow alkyl ethoxylatedalcohol having an average degree of ethoxylation of 80. ³Proxel GXL.

Examples 4-8 are formulations for a heavy duty liquid (HDL) laundrydetergent prepared using the amino silicone nanoemulsion according tothe present disclosure. The amino silicone nanoemulsion is added to theformulations in an amount ranging from 0.001% to 15.0% by weight.

TABLE 8 Ingredient 4 5 6 7 8 emulsions 37-41 0.5 1.0 2.0 1.0 1.0 Sodiumalkyl ether sulfate 20.5 20.5 20.5 C12-15 Alkyl Polyethoxylate (1.1) 9.0Sulfonic Acid Branched alcohol sulfate 5.8 5.8 5.8 Linear alkylbenzenesulfonic acid 2.5 2.5 2.5 1.0 8.0 Alkyl ethoxylate 0.8 0.8 0.8 1.5 6.0Amine oxide 0 0.5 2 1.0 Citric acid 3.5 3.5 3.5 2.0 2.5 Fatty acid 2.02.0 2.0 5.5 Protease 0.7 0.7 0.7 0.4 0.4 Amylase 0.37 0.37 0.37 0.080.08 Mannanase 0.03 0.03 Borax (38%) 3.0 3.0 3.0 1.0 MEA Borate 1.5Calcium and sodium formate 0.22 0.22 0.22 0.7 Amine ethoxylate polymers1.2 0.5 1.0 1.0 1.5 Zwitterionic amine ethoxylate polymer 1.0 2.0 1.0DTPA¹ 0.25 0.25 0.25 0.3 0.3 Fluorescent whitening agent 0.2 0.2 0.2Ethanol 2.9 2.9 2.9 1.5 1.5 Propylene Glycol 3.0 5.0 Propanediol 5.0 5.05.0 Diethylene glycol 2.56 2.56 2.56 Polyethylene glycol 4000 0.11 0.110.11 Monoethanolamine 2.7 2.7 2.7 1.0 0.5 Sodium hydroxide (50%) 3.673.67 3.67 1.4 1.4 Sodium cumene sulfonate 0 0.5 1 0.7 Silicone sudssuppressor 0.01 0.01 0.01 0.02 Perfume 0.5 0.5 0.5 0.30 0.3 Dye 0.010.01 0.01 0.016 0.016 Opacifier² 0.01 0.01 0.01 Water balance balancebalance balance balance 100.0% 100.0% 100.0% 100.0% 100.0%¹Diethylenetriaminepentaacetic acid, sodium salt ²Acusol OP 301.

Examples 9-12 are formulations for powder (granular) laundry detergentsprepared using the amino silicone nanoemulsions according to the presentdisclosure. The amino silicone nanoemulsion is added to the formulationsin an amount ranging from about 0.001% to about 15.0% by weight.

TABLE 9 Ingredients 9 10 11 12 emulsions 37-41 0.5 2.5 5.0 10 Sodiumalkylbenzenesulfonate 16.0000 14.0000 12.0000 7.9 Sodium alkyl alcoholethoxylate — — — 4.73 (3) sulfate Sodium mid-cut alkyl sulfate 1.50001.5000 — Alkyl dimethyl hydroxyethyl — — — 0.5 quaternary amine(chloride) Alkyl ethoxylate 1.3000 1.3000 1.3000 — Polyamine¹ — — — 0.79Nonionic Polymer² 1.0000 1.0000 1.0000 1.0 Carboxymethylcellulose 0.20000.2000 0.2000 1.0 Sodium polyacrylate — — — — Sodiumpolyacrylate/maleate 0.7000 0.7000 0.7000 3.5 polymer Sodiumtripolyphosphate 10.0000 5.0000 — — Zeolite 16.0000 16.0000 16.0000 —Citric Acid — — — 5.0 Sodium Carbonate 12.5000 12.5000 12.5000 25.0Sodium Silicate 4.0 4.0 4.0 — Enzymes³ 0.30 0.30 0.30 0.5 Minorsincluding moisture⁴ Balance balance balance balance¹Hexamethylenediamine ethoxylated to 24 units for each hydrogen atombonded to a nitrogen, quaternized. ²Comb polymer of polyethylene glycoland polyvinylacetate ³Enzyme cocktail selected from known detergentenzymes including amylase, cellulase, protease, and lipase. ⁴Balance to100% can, for example, include minors like optical brightener, perfume,suds suppresser, soil dispersant, soil release polymer, chelatingagents, bleach additives and boosters, dye transfer inhibiting agents,aesthetic enhancers (example: Speckles), additional water, and fillers,including sulfate, CaCO₃, talc, silicates, etc.

Example 13 is an automatic dishwasher powder detergent formulation andexample 14 is an automatic dishwasher gel detergent formulation, bothprepared using the amino silicone nanoemulsions according to the presentdisclosure. The amino silicone nanoemulsion is added to the formulationsin an amount ranging from 0.001% to 15.0% by weight.

TABLE 10 Ingredients 13 14 emulsions 37-41 10  15  Polymer dispersant¹ 53 Carbonate 35-40 0 Sodium tripolyphosphate  0-10  0-25 Silicate solids6  0-10 Bleach and Bleach 4 2-6 activators Enzymes 0.3-0.6 0-1 Disodiumcitrate  2-20 0 dehydrate Nonionic surfactant² 0 0-2 Polygel DKP³ 0 1-2Hydrozincite 0   0-0.3 Zinc Sulfate 0   0-0.8 NaOH 0 0-4 KOH 0  0-15Boric Acid 0 0-4 1,2-propanediol 0 0-1 NaCl 0   0-0.5 Sodium Benzoate 00.1-6   Water, sulfate, perfume, Balance to Balance to dyes and otheradjuncts 100% 100% ¹Anionic polymers, such as Acusol ®, Alcosperse ® andother modified polyacrylic acid polymers. ²Such as SLF-18 Polytergentfrom Olin Corporation. ³Polyacrylate thickener from, e.g., 3V Co.

Examples 15 and 16 are liquid hand dishwashing formulations preparedusing the amino silicone nanoemulsions according to the presentdisclosure. The amino silicone nanoemulsion is added to the formulationsin an amount ranging from 0.001% to 15.0% by weight.

TABLE 11 Ingredients 15 16 C₁₂₋₁₃ Natural AE0.6S 27.0 24.0 C₁₀₋₁₄mid-branched Amine Oxide — 6.0 C₁₂₋₁₄ Linear Amine Oxide 6.0 — SAFOL ®23 Amine Oxide 1.0 1.0 C11E9 Nonionic¹ 2.0 2.0 Ethanol 4.5 4.5 Sodiumcumene sulfonate 1.6 1.6 Polypropylene glycol 2000 0.8 0.8 NaCl 0.8 0.81,3 BAC Diamine² 0.5 0.5 emulsions 37-41 0.5 10 Water Balance Balance¹C₁₁ alkyl ethoxylated surfactant containing 9 ethoxy groups. ²1,3bis(methylamine)-cyclohexane.

Example 17 is a laundry unit dose formulation prepared using the aminosilicone nanoemulsions according to the present disclosure. The aminosilicone nanoemulsion is added to the formulations in an amount rangingfrom 0.001% to 15.0% by weight.

TABLE 12 Ingredients 17 emulsions 37-41 0.5-15 Glycerol (min 99) 5.31,2-propanediol 10.0 Citric Acid 0.5 Monoethanolamine 10.0 Caustic soda— Dequest 2010 1.1 Potassium sulfite 0.2 Nonionic Marlipal C24EO7 20.1HLAS 24.6 Optical brightener FWA49 0.2 C12-15 Fatty acid 16.4 PolymerLutensit Z96 2.9 Polyethyleneimine ethoxylate PEI600 E20 1.1 MgCl2 0.2Enzymes ppm

Examples 18-23 are formulations for hard surface cleaning detergentsprepared using the amino silicone nanoemulsion according to the presentdisclosure. The amino silicone nanoemulsion is added to the formulationsin an amount ranging from 0.001% to 15.0% by weight.

TABLE 13 18 19 20 21 22 23 emulsions 37-41 0.5 2.0 5.0 1.0 10.0 0.3C9/11 EO 8 6.0 7.0 6.0 6.0 C9/11 EO 5 3.5 C12/14 EO21 3.5 C11 EO 5 7.0NaLAS² 2.00 1.8 2.25 NaPS¹ 3.1 3.0 3.0 C12-14AS NaCS³ C12-14 AO⁴ 1.501.50 3.9 2.0 1.25 C12-14 1.0 3.0 Betaine Quaternized 0.1 0.5 0.1 0.2 0.20.05 Alkoxylated PEI HM- 0.76 0.75 0.65 polyacrylate HM-HEC⁵ 0.6 0.8 Xgum 0.42 Na₂CO₃ 0.77 0.75 0.1 0.3 0.2 0.4 Citric Acid 0.046 0.3 0.750.75 0.3 0.3 Caustic Up to Up to Up to Up to Up to Up to 0.46 0.72 0.50.5 0.3 0.65 Fatty Acid 0.40 1.0 0.20 0.50 0.50 0.40 Isofol ® 12⁶ 0.10.2 0.3 0.5 Isofol ® 16⁷ DTPMP 0.30 0.2 DTPA 0.25 0.25 GLDA IPA⁹ 2.0n-BPP¹⁰ 2.0 n-BP⁸ 4.0 2.0 2.0 Minors and up to up to up to up to up toup to Water 100% 100% 100% 100% 100% 100% ¹NaPS is sodium paraffinsulphonate, commercially available from Huls or Hoechst. ²NaLAS issodium linear alkylbenzene sulphonate commercially available from A&W.³NaCS is Sodium Cumene sulphonate commercially available from A&W.⁴C₁₂₋₁₄ AO is a C₁₂₋₁₄ amine oxide surfactant. ⁵HM-HEC is acetylhydroxethylcellulose. ⁶Isofol 12 ® is 2-butyl octanol commerciallyavailable from Condea. ⁷Isofol 16 ® is 2-hexyl decanol commerciallyavailable from Condea. ⁸n-BP is normal butoxy propanol commerciallyavailable from Dow Chemicals. ⁹IPA is isopropanol. ¹⁰n-BPP is butoxypropoxy propanol available from Dow Chemicals.

Examples 24-27 are formulations for rinse-off personal carecompositions, which are multi-phase body wash compositions comprising acleansing phase, e.g., phase containing surfactant, and a benefit phase,e.g., a phase containing moisturizer. These compositions may be easilymodified to contain a single, cleansing phase (for example, asingle-phase, water-based composition generally comprising water,surfactant, perfume, and colorant), instead of cleansing and benefitphases. The following rinse-off personal care compositions may also beeasily modified to contain antiperspirant actives. Water-basedantiperspirant and deodorant compositions (e.g., roll-ons) are known.The amino silicone nanoemulsion according to the present disclosure isadded to the formulations in an amount ranging from 0.001% to 15.0% byweight.

TABLE 14 Ingredient 24 25 Distilled Water Q.S. Q.S. emulsions 37-410.001-15.0 0.001-15.0 Sodium Tridecyl Ether Sulfate 10.54 10.54 DehytonML 6.59 6.59 Electrolyte 4.01 4.01 Iconol TDA3-Ethoxylated TridecylAlcohol 0.84 0.84 Cationic Polymer 0.35 0.35 Sodium Benzoate, NF 0.240.24 pH Adjustment Agent 0.23 0.23 Aqupec Ser W-300C 0.17 0.17 Dissovinena2-s 0.13 0.13 Kathon CG 0.031 0.031 Hydrogen peroxide solution, 20-40%0.004 0.004 Soybean Oil 15 — Petrolatume — 13 Glyceryl monooleate — 2Mercaptopyridine-N-oxide (ZPT) — —

TABLE 15 Ingredient 26 27 Water Q.S. Q.S. emulsions 37-41 0.001-15.00.001-15.0 Guar Hydroxy Propyl Trimonium Chloride 0.2 — AM:TRIQUATCopolymer 0.2 0.2 Sodium Laureth Sulfate, n = 1 10.5 6 Sodium LaurylSulfate — 7 Cocoamdopropyl Betaine 1 1 Ethylene Glycol Disterate 2 2330M silicone 1.1 — Aminosilicone — 1.4 Sodium Chloride Up to 1.5% Up to1.5% Fragrance 0.75 0.75 Preservatives, pH adjusters Up to 1.3% Up to1.3% Zinc Pyrithione 1 1 Zinc Hydroxy Carbonate 1.61 1.61 Petrolatum 1 1Sodium Xylenesulfonate Up to 1% Up to 1%

TABLE 16 Hair Shampoo Compositions All ingredients in % as addedIngredient 28 29 30 Water q.s. q.s. q.s. emulsions 37-41 2 4 10Polyquaterium 76¹ 0.25 0.1 Polquaterium 10² 0.25 GuarHydroxpropyltrimonium 0.2 Chloride⁴ Sodium Laureth Sulfate 21.43 35.71(SLE3S - 28% active)⁵ Sodium Laureth Sulfate 37.93 (SLE1S - 29% active)⁶Sodium Lauryl Sulfate 12.07 24.14 — (SLS - 29% active)⁷ Cocomonoethanolamide⁸ 1.0 0.5 — Cocoamdopropyl Betaine 2.5 — 5.0 (30%active)⁹ Ethylene Glycol Disterate¹⁰ — 1.5 — 330M silicone¹¹ 1.43 1.43 —Silicone microemulsion¹² — — 4 Trihydroxystearin¹³ 0.25 0.25 0.25 SodiumChloride¹⁴ Adjust as Adjust as Adjust as needed for needed for neededfor viscosity viscosity viscosity Fragrance 0.7 0.7 0.7 Preservatives,pH adjusters Up to 1% Up to 1% Up to 1% ¹Acrylamide:Triquat cationicpolymer, tradname: Mirapol AT from Rhodia, ²KG30M cationic cellulosepolymer from Amerchol Dow ³PolyDADMAC, tradename: Mirapol 100S fromRhodia ⁴Jaguar C500 from Rhodia ⁵Sodium Laureth (3 molar ethylene oxide)Sulfate at 28% active, supplier: P&G ⁶Sodium Laureth (1 molar ethyleneoxide) sulfate at 29% active, supplier: P&G ⁷Sodium Lauryl Sulfate at29% active, supplier: P&G ⁸Coco monethanolamide at 85% active, supplier:Stephan Co ⁹Tegobetaine F-B, 30% active, supplier: Goldschmidt Chemical¹⁰Ethylene Glycol Disterate at 100% active, supplier: GoldschmidtChemical ¹¹330 M silicone, 100% active, supplier: Momentive (siliconeused by P&G to make a 70% active, 30 um emulsion) ¹²Belsil 3560 VPsilicone microemulsion from Wacker, 60,000 cst internal viscosity ofsilicone, approx. 125 nm ¹³Thixin R from Rheox Inc. ¹⁴Sodium ChlorideUSP (food grade) from Morton

TABLE 17 Hair Gel Products Ingredient 31 32 33 34 35 emulsions 37-412.00 g 1.00 g 1.00 g 3.80 g 3.80 g Luviset ® Clear 1.00 g 1.50 g 3.00 g1.00 g 1.50 g Luviskol ® VA 64 3.00 g Surfactant 193 1.50 g 1.50 gCarbomer 0.30 g AMP 95% 0.30 g 0.26 g 0.30 g 0.26 g Emulgin L 0.20 gPerfume 0.15 g 0.20 g 0.30 g 0.20 g 0.20 g Natrosol ® G 0.40 g Ethanol16.50 g  18.00 g  34.20 g  5.00 g 4.50 g Aminomethylpropanol 95% 0.10 gaqueous solution Pemulen ® 0.35 g PEG-40 Hydrogenated Castor 0.20 g 0.20g Oil Aculyn ® 48 0.50 g Aquaflex ® SF 40 2.80 g 2.80 gMethylmethoxycinnamate 0.30 g VA/CROTONATES 2.50 g COPOLYMER (Luviset ®CA 66) Sorbitol 4.20 g Direct dye 1.00 g Carbomer (Tego Carbomer) 0.80 gMethylparaben 0.20 g 0.20 g Panthenol 0.10 g Glycerol 5.20 g Propyleneglycol 4.00 g Ammonium 0.35 g Acryloyldimethyltaurate/VP Copolymer(Aristoflex ® AVC) Polysorbate-40 1.00 g PEG-25 PABA 0.50 Water BalanceBalance Balance Balance Balance

TABLE 18 Pump Hair Foams Ingredient 36 37 38 39 emulsions 37-41 0.20 g2.20 g 1.20 g 1.20 g Luviset ® Clear 1.30 g 2.00 g 1.30 g 1.80 g Vinylacetate/crotonic acid 0.30 g copolymer Cocamidopropyl Hydroxysultaine0.40 g 0.20 g 0.40 g 0.40 g Citric acid 0.10 g 0.10 g Ethanol 8.90 g8.90 g 8.90 g Betaine 0.10 g 0.10 g Perfume 0.15 g 0.15 g 0.15 g 0.15 gIngredient Celquat ® L200 0.30 g Direct dye 0.80 g 0.20 g 1.90 gCetyltrimethylammonium chloride 0.20 g Polyquaternium-11 0.30 gPropylene glycol 1.00 g Methylparaben 0.20 g Rosemary leaf extract 0.10g (Extrapon ® Rosemary) Extrapon ® seven herbs - extract 0.10 gPanthenyl ethyl ether 0.10 g Water Balance Balance Balance Balance

TABLE 19 Aerosol and Non-Aerosol Hair Products Ingredient 40 41 42 43 4445 46 emulsions 37-41 4.20 g 5.20 g 3.20 g 1.20 g 0.20 g 1.20 g 2.20 gLuviset ® Clear 1.50 g 1.50 g 2.10 g 2.10 g 1.50 g 2.50 g 1.00 g Butylmonoester of 0.50 g methyl vinyl ether/maleic acid copolymer Butane 4.00g 4.00 g 4.00 g 4.00 g Propane 4.00 g 4.00 g 4.00 g 4.00 g Ethanol 8.90g 8.90 g 2.70 g 28.50 g  28.50 g  PEG-25 PABA 0.40 g 0.40 g 0.70 gBetaine 0.15 g 0.15 g Perfume 0.15 g 0.15 g 0.20 g 0.20 g 0.25 g 0.25 gLaureth-4 0.20 g 0.20 g 0.20 g Cetrimonium bromide 0.05 g Amodimethicone0.50 g Polyquaternium-47 0.50 g 1.00 g 0.50 g Dow Corning 1401 0.25 g2-Ethylhexyl 4- 0.20 g methoxycinnamate Cetrimonium chloride 0.07 g 0.07g 0.20 g Copolymer 845 2.50 g Panthenol 0.20 g 0.20 g 0.35 g Abilquat ®3270 0.70 g Vinyl acetate/crotonic acid 0.60 g copolymer C9-C11 Pareth-80.07 g Aquaflex ® FX-64 1.00 g Polyquaternium-35 1.00 g PEG-40Hydrogenated 0.21 g Castor Oil Octylacrylamide/Acrylates/ 2.00 g 0.65 gButylaminoethyl- methacrylate Copolymer (Amphomer ®) Aminomethylpropanol0.60 g 0.60 g 95% Celquat ® L200 0.20 g Cetyltrimethylammonium 0.20 gchloride Water Balance Balance Balance Balance Balance Balance Balance

TABLE 20 Rinse Out Conditioner Ingredient 47 emulsions 37-41 3.00 gcetyltrimethyl ammonium chloride 1.00 g polymethylphenyl siloxane 1.00 g(CTFA: OUATERNIUM-80; Abil Quat ® 3272) phenoxy ethanol 0.40 gPHB-methylester 0.20 g Copolymer of aminoethyl aminopropyl siloxane anddimethyl 1.00 g siloxane emulsion as a mixture with polyethylenglycolether of tridecyl alcohol and cetyl trimethyl ammoniumchloride (CTFA:AMODIMETHICONE & TRIDECETH-12 & CETRIMONIUM CHLORIDE; Dow Corning 949Cationic Emulsion ®) Isododecane 5.00 g perfume oil 0.40 g Water Balance

TABLE 21 Rinse Out Conditioner Ingredient 48 CETEARYL ALCOHOL 4.50 gCETRIMONIUM CHLORIDE (GENAMIN CTAC 50) 1.30 g Citric acid 0.30 g Perfume0.15 g emulsions 37-41 6.00 g Water Balance

TABLE 22 Leave In Conditioner Ingredient 49 emulsions 37-41 1.00 g2-hydroxy-3-(trimethylamonio)propylether chloride guar gum 0.50 g sodiumbenzoate 0.50 g glyoxylic acid 0.10 g Creatine 0.20 g behenyltrimethylammonium chloride 0.80 g cetylstearyl alcohol 0.60 g stearicacid polyethylenglycol (20 EO) 0.10 g hydrolyzed silk 0.10 g perfume oil0.20 g Water Balance

TABLE 23 Leave In Conditioner Ingredient 50 emulsions 37-41 1.80 gvitamine E-acetate 0.10 g polymethylphenyl siloxane 0.50 g (CTFA:OUATERNIUM-80; Abil Quat^((R)) 3272) propylene glycol 10.00 g  behenyltrimethylammonium chloride 0.50 g sodium chloride 0.05 g d-panthenol0.30 g PHB-propylester 0.30 g Isododecane 2.00 g perfume oil 0.20 gWater Balance

TABLE 24 Split Ends Fluid Ingredient 51 emulsions 37-41 3.50 g vitamineE-acetate 0.10 g polymethylphenyl siloxane 0.50 g (CTFA: OUATERNIUM-80;Abil Quat^((R)) 3272) cyclo penta siloxane (CTFA: CYCLOMETHICONE) 21.00g  dihydroxy polydimethyl siloxane (CTFA: DIMETHICONOL) 2.50 g Ethanol1.50 g perfume oil 0.60 g Water Balance

TABLE 25 Leave In Conditioner Ingredient 52 JAGUAR C-17 0.30 g NATROSOL250 HHR 0.30 g emulsions 37-41 20.00 g  Eumulgin L 0.20 g Perfume 0.15 gPHENOXYETHANOL 0.20 g PHB-METHYLESTER 0.12 g DISODIUM EDTA 0.10 g WaterBalance

TABLE 26 Aerosol Styling mousse Ingredient 53 Polyquaternium-11 (GAFQUAT755 N) 15.00 g  emulsions 37-41 5.00 g Laureth-4 0.40 g Perfume 0.15 gPHENOXYETHANOL 0.20 g PHB-METHYLESTER 0.12 g DISODIUM EDTA 0.10 gPropane/Butane 6.00 g Water Balance

TABLE 27 Volumizing Aerosol Foam Ingredient 54 emulsions 37-41 1.20 gLuviset ® Clear 2.00 g Chitosan 0.27 g Celquat ® L200 1.00 g Pyrrolidonecarboxylic acid 0.23 g Direct dye 0.90 g Laureth-4 0.20 g Cetrimoniumchloride 0.10 g Perfume, preservative 0.50 g Water Balance

The composition is bottled with propane/butane 4.8 bar in the ratio ofactive ingredient solution:propellant gas=94:6 in an aerosol can withfoaming head. Through use of the product on the hair, the hairstyle isgiven long-lasting volume.

Test Methods Time to Wick (T2W) Measurement Method

The fabric Time to Wick property is a measure of the water repellency oroil repellency of a fabric, where longer times indicate greaterrepellency. Water repellency is measured when a drop of water is appliedto the fabric, whereas oil repellency is measured when a drop of oil isapplied to the fabric. The Time to Wick value is measured as follows:The tests are conducted in a well-ventilated lab whose humidity isbetween 40 to 60% RH. and temperature is between 20 to 25° C. Allsamples are preconditioned for at least 24 hours in that lab prior totesting. Untreated control white cotton fabric is prepared from new,100% cotton, woven, white bed sheets, which are de-sized by 3 rounds oflaundering using the AATCC 2003 standard reference liquid detergentwithout optical brighteners (AATCC—American Association of TextileChemists and Colorists, Research Triangle Park, N.C., USA), then cut toyield fabric pieces approximately 10 cm×10 cm in size. Treated testfabric is the same as the untreated control fabric plus the addition ofthe treatment being tested, which is applied to the fabric in accordancewith the manufacturer's instructions, after the de-sizing steps.

On a flat, level hard surface (e.g. benchtop) is placed a fresh squareof a paper towel at least 10 cm×10 cm in size, and on top of that isplaced a square of the prepared fabric. A 300 μL drop of liquid is thendispensed onto the fabric surface from a calibrated pipettor. The dropis DI water when measuring water repellency or it is Canola Oil whenmeasuring oil repellency. The process of absorption of the liquid dropis visually monitored using a video camera such as a Webcam Pro 9000(Logitech, Silicon Valley, Calif., USA), integrated with a laptopcomputer, and displaying either an electronic timestamp or a stopwatchtimer within the field of view, which counts the time elapsed inseconds. The imaging conditions are set up such that the margins of thedrop and the fabric surface are both clearly visible and simultaneouslyin focus, with the viewing angle being from directly above. Nine dropsare administered per fabric square, with each drop placed at a differentlocation separate from all adjacent drops.

The recorded video is used to determine the time—at drop addition andthe time—at drop absorption. For each drop, the time differentialbetween those two time points is calculated and recorded. The time atdrop addition is defined as being the earliest time point at which aportion of the drop is observed making contact with the surface of thefabric. The time at drop absorption is defined as being the earliesttime point at which no portion of the drop is observed rising above thesurface of the fabric. After 60 minutes, the video capture is terminatedregardless of any remaining drops left unabsorbed. Such drops arerecorded as having a time differential of 60 mins. The Time to Wickvalue for a given liquid on fabric is the average of the timedifferentials recorded for 9 drops of that liquid. In order to determinethe effect of a treatment, comparisons are made between the average Timeto Wick value obtained from the treated fabric, versus the averageobtained from its untreated control fabric using the same liquid, wherelonger times indicate greater repellency.

Particle Size Measurement Test Method

Nanoemulsions were diluted with DI water to a concentration of 1% priorto making particle size measurements. The particle size measurements aremade via dynamic light scattering on a model 3D-DLS spectrometerinstrument (LS Instruments, Switzerland). The software accompanying theinstrument (version 6.3, LS Instruments, Switzerland) is used to controlthe spectrometer to acquire data and conduct particle size analysis indynamic light scattering mode. The instrument is set with the followingconditions: Wavelength=632 nm (HeNe laser), scattering angle=90°,Temperature=297 Kelvin (measured by the instrument with sample placed inwater bath and equilibrated for 10 minutes), Integration Time T_(int)=2min, Count rate set between 100-250 kcps (attenuating the laser power),Lag time set between 0.7 microseconds to 50 seconds. All measurementswere taken in autocorrelation mode. All data are reported as thesecond-order Cumulant fit to the autocorrelation function. Thenanoemulsion's particle size is reported as the average diameter valuemeasured, when calculated on a volume-weighted basis. A nanoemulsionwhose particle size is less than 200 nm is defined as being ananoemulsion.

Technical Drying Time Test Method

Switches of human hair, which are of straight low-lift medium brownCaucasian hair, approximately 20 cm long and having approximately 4 g ofhair per switch, are obtained from International Hair Importers &Products (IHIP) (White Plains, N.Y., USA) for use in the Hair DryingTime Test. Use three switches of hair per treatment and per control. Toprepare the hair, measure and record the initial dry weight of each hairswitch, then wash each switch using the following shampoo andinstructions. Hang the switches on a rod above a sink, and wet the hairwith 38° C. DI water until saturated. Squeeze out excess water and applythe specified shampoo, at a dosage of 0.1 g shampoo per 1 g hair (drywt). Apply half the total amount of shampoo on one side of the switchand rest on the other side. Massage the hair switches by hand for 60seconds to create lather throughout the switch. Rinse thoroughly with38° C. DI water running at 4 to 6 L/min for at least 2 minutes (1 minper side). Use hand manipulation to squeeze out the excess water. Up to35 g of hair can be shampooed simultaneously. Each ingredient in theshampoo is listed below at its final concentration in percent by weight:

Shampoo Ingredients Wt % Sodium Lauryl Sulfate 5.0 Sodium LaurethSulfate 10.0 Cocamidopropyl betaine 0.8 Guar Cationic Polymer 0.5Extracts of Camellia Sinensis 2.1 Leaf, Citrus Auranfium Dulcis Flower,Zea Mays Silk. Sodium Citrate 0.4 Sodium EDTA 0.16 Citric Acid 0.04Sodium Benzoate 0.25 DI Water to balance to 100%

The remaining steps in the hair dying time test method are conducted inan air conditioned room having a temperature of 20 to 25° C., and arelative humidity of 40 to 60% RH, and are conducted in immediatesuccession without any delays or pauses between steps. Apply thetreatment product being tested onto just one hair switch at a time,using switches prepared and shampooed as specified above. Prior toapplying the treatment, ensure that the hair switch is thoroughlysaturated with 38° C. DI water but is not dripping. Place the switch ina plastic weighing-boat dish approximately 13 cm×13 cm, and dose the wethair with 1 g of the treatment solution being tested per 4 g of hair dryweight. Apply the treatment solution homogenously along the length ofthe hair. Massage the treatment solution into the hair switch in thedish for 3 minutes with hand manipulation, ensuring that all the hairfibers are exposed to the solution. The switch is then subjected tomultiple cycles of blow drying and weighing, where the duration of blowdrying and the subsequent switch weight are recorded for each cycle, andare compared to the switch's initial dry weight. Hang the hair switchvertically and commence blow drying while the hair is still thoroughlysaturated with water and treatment solution. Blow dry the hair switchusing a Sunbeam 1600 Watt hand-held electric hair dryer with diffusernozzle adapter, with the heat level selection set on High, (SunbeamCorporation Limited, Botany, Australia), and positioned 7 cm away fromthe hair. After 3 minutes of blow drying (1.5 mins per side), weigh thehair switch and record the weight. Press the hair switch gently betweentwo kitchen paper towels for 2 seconds and reweigh. Repeatedly blow dryand reweigh the hair again using drying time increments of 30 secondsfor each cycle. When the switch weight approaches its initial dryweight, reduce the drying time increments to 20 seconds for eachsubsequent cycle, and continue the drying and weighing cycles until thehair switch returns to its initial dry weight. The switch's total hairdrying time is determined by summing all of the drying times that wererequired to return the hair to its initial dry weight. This cumulativevalue is the switch's Hair Drying Time. The hair drying times obtainedfrom the three replicate switches in each treatment are averaged todetermine the mean hair drying time for the treatment. To determine theeffect of the treatment on hair drying time, the mean hair drying timefor the treatment is compared to the mean hair drying time obtained from3 control switches, which were each dosed with 1 g of DI water insteadof 1 g of treatment solution.

The above Technical Dry Time Test Method is also relevant to skin.

Contact Angle Test Method

The static contact angle of a nanoemulsion is determined by measuring asessile droplet of water placed on a nanoemulsion-coated surface, asmeasured via an optical profile image of the droplet. The surface isprepared using 2.5 cm×2.5 cm sized silica wafers (J#19777), as availablefrom Silicon Valley Microelectronics Inc. (SVM), (Santa Clara, Calif.,USA). Clean the wafers by rinsing with DI water followed by furtherrinses with ethanol and then with acetone, ensuring that both theorganic solvents are of a high purity grade such as that suitable foruse in LC-MS analyses. Expose the wafers to ozone for 15 minutes, byplacing a cleaned wafer into a specimen chamber attached to an ozonegenerator such as the UV/Ozone Pro Cleaner™ (manufactured by BioforceNanoscience, Ames, Iowa, USA). The nanoemulsion to be tested is thenspin-coated onto the cleaned and ozonated wafers. To achieve thiscoating, prepare the emulsion to be tested at a concentration of 500 ppmin DI water. Dispense 1600 μL of the nanoemulsion onto a silica wafer,wait 1 min then spin the wafer at 2000 rpm for 30 seconds in a spincoater instrument, such as the WS-400B-6NPP/Lite/AS2 (manufactured byLaurell Technology Corporation, North Wales, Pa., USA). The spin-coatedwafer is the then allowed to cure for 24 hours at room temp or in an 80°C. oven for 1 hour. With the wafer at room temperature, use a contactangle goniometer such as the FTA 200 manufactured by First TenAngstroms, Inc, Portsmouth, Va., USA), to measure the static contactangle of a sessile 10 μL drop of DI water placed onto the coated surfaceof the silica wafer. Prepare and measure 3 replicate spin-coated wafersfor each nanoemulsion to be tested, and average the replicate contactangle results to obtain the contact angle for that nanoemulsion. Thecontact angle of the cleaned but uncoated silica wafer is 36°.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A method of making an amino silicone nanoemulsioncomprising the steps of: a) mixing one or more liquid amino siliconecompounds represented by formula (1) below with a solvent:

where each R is an alkyl group or a phenyl group with 1-10 carbon atoms,wherein each R′ is an alkyl group having 1-10 carbon atoms, a phenylgroup, a monovalent group represented by formula (2) below, or amonovalent group represented by the formula: —OR³, where R³ is ahydrogen atom or a monovalent hydrocarbon group with 1-10 carbon atoms;m is a whole number from 50-1000, n is a whole number from 1-100, A is amonovalent group represented by formula (2) below:—R¹—(NH—R²)a-NH₂  (2) where R¹ and R² are divalent hydrocarbon groupswith 1-10 carbon atoms; a is a whole number from 0-4; b) mixing saidmixture of amino silicone and solvent with surfactant, water, and,optionally, a protonating agent, to form a nanoemulsion; c) dividingsaid nanoemulsion into a first nanoemulsion and a second nanoemulsion;d) mixing said second nanoemulsion with a non-resin crosslinking agenti. at a temperature ranging from about 20° C. to about 100° C.; ii.wherein said non-resin crosslinking agent is represented by formula (3):R-L_(n)  (3) wherein n≧2, R is a polyvalent, saturated or unsaturated,substituted or unsubstituted, organic moiety comprising 2-30 carbonatoms, and the L groups, which may be identical or different, arefunctional groups capable of reacting with amino groups; iii. whereinthe molar ratio of said non-resin crosslinking agent to said liquidamino silicone compound in said second nanoemulsion is from about 0.05:1to about 10:1; e) mixing said first nanoemulsion with said secondnanoemulsion to form a third nanoemulsion.
 2. The method of claim 1wherein the molar ratio of said non-resin crosslinking agent to saidliquid amino silicone compound in said second nanoemulsion is from about0.1:1 to about 5:1.
 3. The method of claim 1 wherein the molar ratio ofsaid non-resin crosslinking agent to said liquid amino silicone compoundin said second nanoemulsion is from about 0.5:1 to about 3:1.
 4. Themethod of claim 1 further comprising the step of mixing said firstnanoemulsion with a non-resin crosslinking agent: i. at a temperatureranging from about 20° C. to about 100° C.; ii. wherein said non-resincrosslinking agent is represented by formula (3):R-L_(n)  (3) wherein n≧2, R is a polyvalent, saturated or unsaturated,substituted or unsubstituted, organic moiety comprising 2-30 carbonatoms, and the L groups, which may be identical or different, arefunctional groups capable of reacting with amino groups; iii. whereinthe molar ratio of said non-resin crosslinking agent to said liquidamino silicone compound in said first nanoemulsion is from about 0.05:1to about 10:1, preferably from about 0.1:1 to about 5:1, more preferablyfrom about 0.5:1 to about 3:1.
 5. The method of claim 4 wherein themolar ratio of said non-resin crosslinking agent to said liquid aminosilicone compound in said first nanoemulsion is from about 0.1:1 toabout 5:1.
 6. The method of claim 4 wherein the molar ratio of saidnon-resin crosslinking agent to said liquid amino silicone compound insaid first nanoemulsion is from about 0.5:1 to about 3:1.
 7. The methodof claim 4 wherein the ratio of said non-resin crosslinking agent tosaid liquid amino silicone compound in said first nanoemulsion isdifferent from the ratio of said non-resin crosslinking agent to saidliquid amino silicone compound in said second nanoemulsion.
 8. Themethod according to claim 1 wherein the ratio of said first nanoemulsionto said second nanoemulsion in said third nanoemulsion is from about 1:1to about 12:1, preferably about 6:1.
 9. The method according to claim 1wherein said third nanoemulsion is substantially free of a siliconeresin.
 10. A treatment composition that comprises a. an amino siliconenanoemulsion made according to the method of claim 1, b. a carrier,wherein said treatment composition comprises from about 0.001% to about15% amino silicone nanoemulsion, by weight of the treatment composition,and said treatment composition is substantially free of silicone resin.11. The treatment composition of claim 10, wherein said treatmentcomposition is selected from the group consisting of beauty carecomposition, hand washing composition, body wash composition, shampoocomposition, conditioner composition, cosmetic composition, hair removalcomposition, oral care composition, laundry spray composition, laundryrinse additive composition, liquid laundry detergent compositions, solidlaundry detergent compositions, hard surface cleaning compositions,liquid hand dishwashing compositions, solid automatic dishwashingcompositions, liquid automatic dishwashing, and tab/unit dose formautomatic dish washing compositions, and laundry detergent compositionscontained in a water-soluble pouch.